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CROSS REFERENCE TO RELATED APPLICATIONS
This is a continuation of PCT application No. PCT/EP2013/002676, entitled “METHOD FOR OPERATING AN INTERNAL COMBUSTION ENGINE”, filed Sep. 5, 2013, which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a method for operating an internal combustion engine, in particular an internal combustion engine with allocated subsequent exhaust gas treatment.
2. Description of the Related Art
In internal combustion engines which are also referred to as combustion engines, mechanical energy is generated through combustion of a fuel-air mixture in a combustion chamber, typically a cylinder. Such internal combustion chambers, whether they are powered by diesel or gasoline are used to drive devices.
Exhaust gas treatment is to be understood as all methods wherein combustion gases are cleaned mechanically, catalytically or chemically after they have left the combustion chamber.
In order to ensure safe operation of the internal combustion engine and thereby the driven device it is necessary to record and evaluate certain variables, for example physical variables of the internal combustion engine, of the exhaust gas treatment system and of additional components at regular time intervals or even continuously. Some variables are also controlled or regulated. Physical variables are generally quantitatively determinable properties of a physical object.
Variables of the internal combustion engine are understood to be for example the rotational speed of the internal combustion engine, the speed of the device and the exhaust gas temperature. These variables are however only cited as an example here.
It is thus provided for example to increase the exhaust gas temperature as a variable as a measure to regenerate the diesel particle filter. This occurs controlled, or by establishing a target value in one adjustment. If this measure occurs for example too early through the load profile locally by the user of the vehicle this can result in unnecessarily high fuel consumption.
What is needed in the art is a method of improving the operation of an internal combustion engine, where applicable, with an allocated exhaust gas treatment system.
SUMMARY OF THE INVENTION
The method of the present invention is intended for the operation of an internal combustion engine, wherein a first distribution of values for at least one variable is used and a second distribution of these values is determined in that, over a second time period values for this variable are recorded and classified. This first distribution is then compared with the second distribution. Classification is understood to mean that the values are assigned to categories, normally to value ranges. This results in a static distribution of the values.
Variables can be physical or physically measurable variables, but also model-based other variables. Physical variables, for example the rotational speed of the internal combustion engine or the exhaust gas temperature, if applicable together with other variables describes an operational condition of the internal combustion engine and/or the exhaust gas treatment system, and thereby the operated device.
The arrangement determines the first distribution by recording of values of the at least one variable over a first time period. As a rule this occurs by means of a distribution function which allocates the determined values to categories, in other words classifies them, thus determining a static distribution in this manner.
The first time period is appropriately longer than the second time period. The first time period may for example be seven days, the second time period five hours.
The first distribution in one category can alternatively be factory-predetermined. This predetermined classification can of course be adapted during operation of the device.
An additional arrangement of the method provides that, in the second distribution the at least one variable is classified dependent on at least one second variable. In this manner dependencies between variables in the device can be considered. A dependent distribution function is used for this.
It may moreover be provided that an event is triggered on the basis of the comparison. This event may for example be that, when the exhaust gas temperature is considered as variable the exhaust gas temperature is not changed or is changed to a different extent.
In one design form of the method a threshold is considered. This means that only at a certain level of deviation of the first distribution from the second distribution this is classified as a deviation, triggering an event if applicable.
It is therefore suggested to implement the method for a system including an internal combustion engine with an allocated exhaust gas treatment system.
The suggested arrangement is used in combination with the driven internal combustion engine, for example in a driven device and is designed to implement a method of the type described previously. The arrangement includes a control device which is designed for comparison of a first distribution with a second distribution.
A classifying statistical evaluation method is hereby performed to generally optimize online operating costs for systems which include an internal combustion engine and an exhaust gas treatment system.
The presented method is basically conceivable for a system with exhaust gas treatment system. In this manner the consumption, for example the diesel consumption of an engine can be reduced. The internal combustion engine can adapt to the current engine operating profile, without thereby jeopardizing the safety of the system.
Certain variables of the engine are hereby classified into categories and a distribution is established in an arrangement over two different time periods. The behavior over the two different time periods is processed further based on the model. The result can then moreover be statistically evaluated and depending on probability of a certain result, an action can be activated or delayed.
The method serves automated optimization of the operating costs for the internal combustion engine. It is advantageous that the fuel consumption can be reduced during operation of the engine. Due to the load profile, on-site with the customer, measures for regeneration of the diesel particle filter, namely increasing of the exhaust gas temperature, in other words high diesel consumption could for example be started too soon. If such measures are somewhat delayed it is conceivable that no regeneration measures become necessary if, for example an engine operating point with high exhaust gas temperatures occurs again, which is statistically expected.
Additional possible applications are given for example in the case of a premature regeneration for reducing the exhaust gas backpressure and for the efficiency calculation of the regeneration measures.
Additional advantages and arrangements of the invention result from the description and the enclosed drawings.
It is understood that the aforementioned properties and the properties yet to be explained below can be used not only in the respectively specified combination, but also in other combinations or on their own without leaving the scope of the current invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The above-mentioned and other features and advantages of this invention, and the manner of attaining them, will become more apparent and the invention will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein:
FIG. 1 illustrates a flow chart of one design form of the described method;
FIG. 2 illustrates a flow chart of an additional design form of the described method;
FIG. 3 illustrates a flow chart of yet an additional design form of the described method; and
FIG. 4 is a strongly simplified schematic illustration of a design form of a device in which the suggested method would be implemented.
Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrate embodiments of the invention, and such exemplifications are not to be construed as limiting the scope of the invention in any manner.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIG. 1 , values Gn, k for a variable G which describes a physical property of an internal combustion engine enter into a relative distribution function 10 which issues an n * classification, namely a first distribution Y1n, k over a first time period which is limited. If the first time period is selected sufficiently long, then the long-term behavior of the internal combustion engine can be described therewith.
Values Gn, k are also entered into a dependent distribution function 12 for a second time period which is generally shorter than the first time period. Moreover, values Xn, k are entered for an additional variable X. This results in a second distribution Y2n, k, which describes a short-term behavior of the internal combustion engine, in this case dependent on an additional variable. Thus, variable G is evaluated or respectively classified dependent on variable X, which is influenced for example by the behavior of the user. Second distribution Y2n, k represents an n * classification. This can be performed time-limited or unlimited.
In a model 14 a comparison occurs between the first distribution Y1n, k and the second distribution Y2n, k. The result of the comparison is subsequently evaluated (block 16 ) and information is issued at an output 18 which triggers an event when applicable.
The method therefore statically captures the influence of certain variables through the behavior of the user or respectively the customer. The effects of this influence are calculated in order to adapt the behavior of the entire system, for example the internal combustion engine with allocated exhaust gas treatment system, if necessary.
The same classification occurs hereby for relative distribution function 10 and independent distribution function 12 . It is determined, depending on Gn, k in which category the system, for example the internal combustion engine and exhaust gas treatment system are operated at any time.
The following applies therein:
k=1, 2, . . . 5 category D=0, 1, 2 damping L>1 learning component
For the case that Gn, k is within a category k:
Y 1 n,k=Y 1 n− 1, k +( Xn,k−Y 1 n− 1 ,k ) /L
For the case that Gn, k is outside a category k:
Y 2 n,k=Y 2 n− 1, k +( Y 2 n− 1, k )* D/L
FIG. 2 illustrates an additional possible version of the method. The illustration shows a relative distribution function 30 and a dependent distribution function 32 .
In relative distribution function 30 an exhaust gas temperature distribution is determined over a long time period. In dependent distribution function 32 an exhaust gas temperature distribution is determined over a short time period.
Input variables are values for exhaust gas temperature Gn, k and values Xn, k for an additional variable X which in this case is a constant 1 .
It can be seen that values Gn, k are allocated to categories 200° C., 250° C., 300° C., 350° C. and 400° C. All values Gn, k which are less than or equal to 200° C. can hereby for example be allocated to category 200° C. Alternatively, all values Gn, k which are less than 250° C. can be allocated to category 200° C. In this case all values Gn, k which are greater than or equal to 250° C. and less than 300° C. are allocated to category 250° C. This can however be agreed upon as desired.
The resulting distributions are evaluated (block 34 ), whereby also only certain categories may be examined. For example, only categories>350° C. may be examined during the evaluation. A threshold 36 is imposed on the result of the evaluation. In this case it is recognized that considerably more values are allocated to category 400° C. which results from the relative distribution function 30 , than to category 400° C. which results from the dependent distribution function 32 . Since consequently high exhaust gas temperatures are expected in the foreseeable future, the regeneration is initially suppressed and corresponding information is provided at an output 38 .
In this case the method is based on the following considerations:
If there has not been a phase with high temperature for a long time, but if this is normally the case, the probability for one to occur soon increases. Consequently, a limited delay of the soft thermo-management occurs.
FIG. 3 shows an additional design of the method with a relative distribution function 50 which determines a first distribution over a long time period, and a dependent distribution function 52 which determines a second distribution over a short time period. Input variables are values Gn, k for an exhaust volume. Additional input variables for the dependent distribution function 52 are values Xn, k for a differential pressure.
Relative distribution function 50 which determines a first distribution over a long time period detects in which exhaust gas volume category the internal combustion engine is situated. Dependent distribution function 52 which determines a second distribution over a short time period detects in which exhaust gas volume category the internal combustion engine experiences what level of additional differential pressure dP.
In a model 54 the differential pressure is correlated with a change in consumption. Finally a weighting by comparison is conducted (block 56 ) and information in regard to additional consumption dependent on the differential pressure is provided at an output 58 .
Depending therefore on how often the internal combustion engine is in which exhaust gas category, an additional differential pressure can be determined through the diesel particle filter.
FIG. 4 illustrates in a strongly simplified schematic depiction a device which is identified with reference number 70 .
The illustration shows an internal combustion engine 72 which is provided to drive device 70 and to which an exhaust gas treatment system 74 is allocated. In addition a controller 76 is provided which is connected with a number of sensors 78 to detect physical variables.
In controller 76 a comparison can be performed between a first distribution 80 which can be determined with a relative distribution function over a first time period, and a second distribution 82 which can be determined over a relative distribution function or a dependent distribution function over a second time period.
While this invention has been described with respect to at least one embodiment, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
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The invention relates to a method and an arrangement for operating an internal combustion engine. In the method a first distribution of values for at least one variable is used, the variable describing a physical property of the internal combustion engine, and over a second time period values for this variable are recorded and classified, such that a second distribution is determined. The first distribution is then compared with the second distribution such that the behavior of the internal combustion engine can be adapted on the basis thereof.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
2. Description of the Related Art Including Information Disclosed Under 37 CFR 1.97 and 1.98.
The invention relates to a method for finding the position of a communications device, and to a communications device for carrying out the method.
Future portable or car telephones will offer the capability, for example in the event of an accident or some other emergency situation, to send a short message automatically or manually to a service provider, with the position of the telephone also being transmitted at the same time.
Present-day traffic telematics systems provide for the last four known position information items, for example from a GPS receiver which can be installed in a motor vehicle, for example, to be transmitted to the service provider. A number of position information items have to be transmitted in order to confirm the direction in which the vehicle was last moving in order, for example, to allow a rescue vehicle to be sent onto the motorway in the correct direction, immediately and in the event of accidents on motorways.
However, this does not take account of the fact that the accuracy of the GPS position information fluctuates widely.
The invention is based on the object of specifying a method in order to allow more accurate position information relating to the communications device to be provided when required or in an emergency. Furthermore, a communications device for carrying out the method is intended to be provided.
BRIEF SUMMARY OF THE INVENTION.
Claim 1 contains a solution relating to the method of the set object. In contrast, claim 11 specifies a solution relating to an apparatus for the set object.
In the case of a method according to the invention for finding the position of a communications device, this device receives position data together with association position accuracies, in which case, in order to determine optimum positions, the communications device stores a number of such most recently received position data items whose position accuracy is better than a predetermined position accuracy.
Thus, in the case of the invention, position information which is subject to excessively high inaccuracy is not used any further and only position information with a high accuracy level is passed on to the service provider, in order to allow the communications device, or a person carrying it or a vehicle in which it is located, to be found more reliably when required or in an emergency.
In order to determine the optimum positions, the route on which the communications device is moving is expediently subdivided into sections. These may be predetermined journey distances or sections defined by predetermined time periods. An optimum position can then be determined for each of these sections so that, for example, four optimum positions can continuously be stored for four successive sections, for example in a memory in the form of a shift register. The number of buffer-stored optimum positions could also be greater than four.
Thus, to be more precise, a respective one of the optimum positions can be determined along in each case one predetermined journey distance, for example, or a respective one of the optimum positions can be determined in in each case one predetermined time period.
When determining the respective optimum positions in the respective sections (path or time sections), the predetermined position accuracy can also be changed, in order to obtain the best-possible optimum positions.
Thus, according to a refinement of the invention, within the predetermined journey distance or the predetermined time period, the predetermined position accuracy can be replaced by such a position accuracy from position data which are supplied later, which position accuracy is better than the predetermined position accuracy. This allows the best or the most accurate position in the respective path or time section to be found in a simple manner, which is then buffer-stored.
In this case, the predetermined position accuracy can be reset to a new (identical) initial value at the start of each predetermined journey distance or at the start of each predetermined time period, which initial value is then once again set to be somewhat greater than the best position accuracy from the previous section in order initially to allow an optimum position to be detected once again at all in the present section.
The initial value of the position accuracy can, of course, also be changed from section to section for a respective section, for example to match the actual geographical conditions.
If required, at least those optimum positions are transmitted to a service provider which have been determined for predetermined journey distances or predetermined time periods which have been completed.
However, in order to make the finding of the communications device when required or in an emergency even more reliable, it is also possible additionally to transmit to the service provider that optimum position which has been determined, when the requirement or the emergency occurred, for a predetermined journey distance or predetermined time period which had not yet been completed.
Furthermore, in another refinement of the invention, the most recently received position information when the requirement or emergency occurred is transmitted to the service provider as well, even if its position accuracy is poorer than the predetermined position accuracy. Even such position information with relatively poor position accuracy can provide a good indication of the actual location of the communications device, since this position information is associated with a position which is very close to the communications device.
A communications device which receives position data together with associated position accuracies contains a selection device for selecting a number of such most recently received position data items whose position accuracy is better than a predetermined position accuracy, as well as a memory device in order to store the position data selected in this way, as optimum positions. If an optimum position occurs in each case for successive path sections or time sections, then successive optimum positions can be passed through a memory which has a specific number of memory locations, for example being pushed through a memory having four memory locations, so that the last four or latest optimum positions are always available so that, if required or in an emergency, they can be transmitted to a service provider.
In this case, the communications device may have a switching device by means of which, when required or in an emergency, the memory device can be connected to a transmitter, via which the optimum positions are then transmitted to the service provider.
Furthermore, the selection device can set a time period for the selection of the position data as a function of control signals which can be produced once the communications device has travelled through predetermined journey distances, or once predetermined time periods have elapsed. The route of the communications device is thus subdivided by the control signals into the sections already mentioned above.
The position data together with the position accuracies may come directly from a satellite-aided radio navigation appliance (for example a GPS receiver), or may be determined by the communications device by measuring the delay time of signals coming from different base stations.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S).
An exemplary embodiment of the invention will be explained in detail in the following text with reference to the drawing, in which:
FIG. 1 shows a motor vehicle journey route with position data of varying position accuracy;
FIG. 2 shows a block diagram of the apparatus according to the invention for selecting and buffer-storing optimum positions along the motor vehicle journey route; and
FIG. 3 shows a flowchart to explain the selection and buffer-storage of optimum positions along the motor vehicle journey route.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows a journey route 1 travelled by motor vehicle that is not illustrated. The motor vehicle is assumed to be equipped with a radio navigation appliance, for example with a GPS or satellite navigation appliance. The GPS navigation appliance contains a GPS receiver which uses received satellite signals to produce position data at its output. Such position data comprise, for example, X-and Y-coordinates to identify positions 2 , 3 , 4 , 5 , 6 and 7 along the journey route 1 . The position data for the respective positions 2 - 7 appear at periodic intervals at the output of the GPS receiver, for example once a second. In addition to the respective position data, the GPS receiver supplies at its output associated position accuracies 8 in the form of characteristic values, for example values ΔX, ΔY, in order to characterize the precision of the respective position data. These position accuracies 8 are shown in FIG. 1 in the form of circles around the respective GPS positions. They can also be specified by the radius or diameter of the respective circles. The diameter has been chosen in FIG. 1 .
Thus, if the motor vehicle moves along the journey route 1 in the direction of the arrow that is shown, then the position data 2 with the associated position accuracy appear first of all at the output of the GPS receiver. After this, the position data 3 with a position accuracy that is now better (circle with a smaller diameter) appear at the output of the GPS receiver while, after this, the position data 4 appear, whose position accuracy is poorer (circle with an even larger diameter), etc.
Corresponding to the present invention, however, the position data items 2 - 7 along the journey route 1 of the motor vehicle are not all permanently buffer-stored, but only a predetermined and small number of those position data items whose position accuracy is better than a predetermined position accuracy. This relates to the position data items 3 , 5 and 7 shown in FIG. 1 . In the following text, these will be referred to as the selected position data or optimum positions.
In order to allow these optimum positions to be found, the journey route 1 is first of all subdivided into predetermined sections, as is indicated by the transverse bars 9 , 10 and 11 . These sections may be sections of equal distance length along the journey route 1 , which can be set by measuring the distance travelled by the motor vehicle. Distance sensors could be located on the vehicle for this purpose, in each case supplying a control signal after a predetermined travel distance, to indicate that one of the said sections has now been passed through. In FIG. 1, the control signals appear at the positions of the transverse bars 9 , 10 and 11 .
However, the journey route 1 could just as well also be subdivided into time sections, for example by a counter running cyclically from an initial value to a final value, and supplying an appropriate control signal on reaching the final value.
In each of the previously defined sections (distance or time period), those position data items are then in each case sought whose position accuracy is better than the predetermined position accuracy. If the said journey distance sections or time periods along the journey route 1 were relatively long, then it would be possible to store position data for a number of positions per section, provided they satisfy the condition mentioned above with regard to position accuracy. Position data whose position accuracy is poorer than the predetermined position accuracy are excluded.
If, on the other hand, the said sections (journey distance sections or time periods) are relatively short, it would also be possible to store, per section, the position data for only one position in each case that satisfied the abovementioned condition for position accuracy. In order to determine these position data items and the optimum positions, the requirements for the position accuracy are in this case increased in steps so that, in the end, those positions are found in each section which have the best position accuracy in that section. FIGS. 2 and 3, below, relate to such a version.
FIG. 2 shows a block diagram of the apparatus according to the invention having a GPS receiver 12 , a selection device 13 for selecting optimum positions, a memory device 14 for storing current positions, optimum positions and selected optimum positions, a transmitter 15 for transmitting positions stored in the memory device 14 to a service provider 16 via a radio path 17 when a predetermined event occurs, as well as having a switch 18 for transmitting position data from the memory device 14 to the transmitter 15 .
If the motor vehicle travels in the direction of the arrow over the journey route 1 shown in FIG. 1, then the position data X, Y for the positions 2 to 7 appear successively at the output of the GPS receiver 12 . These position data items are stored successively in a memory 14 a as current positions, together with the associated position accuracies in each case. In this case, there is only one data record in the memory 14 a at a time, in each case comprising the position data with the associated position accuracy for only one position.
The selection device 13 is used to look for the respective optimum position (which has the best position accuracy in this section) for in each case one journey distance section or time section along the journey route 1 . In this case, the best position accuracy means that this is better than all the other position accuracies in this section that are better than the predetermined position accuracy. The optimum position selected by the selection device 13 is then stored in a memory 14 b in the memory device 14 . Thus, at the moment, there is also only one data record in the memory device 14 b , namely the position data selected per route section for only one position, together with the associated position accuracy.
Such successive optimum positions are also stored by the selection device 13 in a memory 14 c in the memory device 14 for a number of successive route sections (journey distance sections or time length sections). This memory 14 c thus contains n data records, in which case n may be, for example, four. If the vehicle travels over a fifth route section, then the selected optimum position for the first route section is automatically erased, and so on, so that only four data records are available at all times.
If a predetermine event occurs, for example the motor vehicle travelling along the journey route 1 is involved in an accident, then this is reported to the transmitter 15 via an input 15 a . This may be done automatically or manually. The contents of the memory devices 14 a , 14 b and 14 c are then transmitted via the switch 18 to the transmitter 15 which, for its part, transmits the position data obtained in this way via a radio link 17 to a service provider 16 , for example to a recovery service, police station, or the like.
If, for example, an accident were to occur at the time T in FIG. 1, then the memory 14 c would contain the position data for the positions 3 and 5 , the memory 14 b would contain the position data for the position 7 , and the memory 14 a would either also contain the position data for the position 7 or for a position which, starting from the position 7 and along the journey route 1 have been determined by a device connected to the motor vehicle, for example via a distance sensor (dead-reckoning method). This last-mentioned position together with the position data for the positions 3 , 5 and 7 would then be sent to the service provider 16 , if an event occurred, so that the service provider 16 would have the option of locating the motor vehicle accident position very accurately and of exactly defining the route to the accident location.
FIG. 3 shows a flowchart illustrating how the apparatus according to the invention operates. This flowchart will be explained in conjunction with FIGS. 1 and 2, starting at the position 2 . In this case, it is assumed that the position data for the position 2 have a position accuracy, which is equal to the predetermined position accuracy. This is the position accuracy 8 in this case.
Thus, in step S 1 in FIG. 3 the position data for the current position 2 are first of all loaded, together with the associated position accuracy. These items are buffer-stored in the memory 14 a . After this, a check is carried out in step S 2 to determine whether the distance (predetermined journey distance or predetermined time period) has already been exceeded. Generally speaking, this is not the case since the bar 9 in FIG. 1 has not yet been reached. The subsequent step S 4 is thus reached.
A check is carried out in step S 4 to determine whether the current position accuracy for the position 2 is better than the predetermined position accuracy. This is not the case for the position 2 since, on the basis of the agreement, its position accuracy should be equal to the predetermined position accuracy. The procedure thus returns to step S 1 .
The position data for the position 3 are now loaded, together with the associated position accuracy, in step S 1 . These items are buffer stored in memory 14 a . Since the bar 9 has not yet been reached, the following step S 4 is actioned. In step S 4 it is now found that the current position accuracy for position 3 is better than the predetermined position accuracy, as is indicated by the smaller circle in FIG. 1 . Step S 5 is thus reached.
In step S 5 , the optimum position in the memory 14 b is replaced by the current position. At the same time, the predetermined position accuracy is replaced by the current position accuracy, so that the requirements for the position accuracy of the subsequent positions are increased. After this, the procedure returns to step S 1 .
The position data for the position 4 are now loaded, together with the associated position accuracy, in step S 1 . These items are buffer stored in the memory 14 a.
It is then found in step S 2 that the distance has been exceeded. The predetermined journey distance has thus been travelled, or the time period has been exceeded. The following step S 3 is thus reached. In step S 3 , the position 3 is now stored as the optimum position in the memory 14 c . At the same time, the predetermined position accuracy is preloaded again, that is to say it is reset to the old value.
After this, a check is carried out in step S 4 to determine whether the current position accuracy, that is to say that for the position 4 , is better than the predetermined position accuracy. This is not the case for the position 4 (circle having a very large radius), so that the process returns to step S 1 .
In step S 1 , the position data for the position 5 are now loaded together with the associated position accuracy. These items are buffer stored in the memory 14 a.
In step S 2 , it is found that the distance has not yet been exceeded, since the bar 10 has not yet been reached. Step S 4 is thus now reached.
In step S 4 , it is found that the current position accuracy, that is to say that of position 5 , is better than the predetermined position accuracy, so that the step S 5 is then reached.
In step S 5 , the optimum position in the memory 14 b is now replaced by the current position (position 5 ). At the same time, the predetermined position accuracy is replaced by the current position accuracy, that is to say by that of the position 5 . After this, the process returns to step S 1 .
In step S 1 , the position data for the position 6 are then loaded together with the associated position accuracy. These items are buffer stored in the memory 14 a.
It is now found in step S 2 that the bar 10 has been passed, so that step S 3 is then reached.
In step S 3 , the optimum position, that is to say the position 5 , is stored as the second position in the memory 14 c.
At the same time, the predetermined position accuracy is preloaded again in step S 3 , that is to say is set to the old value.
After this, a check is carried out in step S 4 to determine whether the current position accuracy for the position 6 is better than the previous (old) position accuracy. This is not the case, so that the process returns to step S 1 again.
In step S 1 , the position data for the position 7 are then loaded-together with the associated position accuracy. These items are buffer stored in the memory 14 a.
Since the bar 11 has not yet been reached, step S 4 is then actioned.
In step S 4 , it is found that the current position accuracy of the position 7 is better than the predetermined position accuracy, so that step S 5 is then reached.
In step S 5 , the optimum position in the memory 14 b is replaced by the current position, and the predetermined position accuracy is in turn replaced by the current position accuracy.
After this, the process normally returns to step S 1 , and the next position is loaded, etc.
However, if the abovementioned event occurs at the time T, the contents of the memories 14 a , 14 b and 14 c are sent to the service provider 16 , that is to say, in this case, if no dead-reckoning method is used, the position 7 as the current position from the memory 14 a , the position 7 as the optimum position from the memory 14 b , and the positions 3 and 5 as selected optimum positions from the memory 14 c.
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In order to find the position of a communications device, this communications device receives position data ( 2 - 7 ) together with associated position accuracies ( 8 ). In order to determine optimum positions ( 3, 5, 7 ), the communications device stores a number of such most recently received. position data items whose position accuracy ( 8 ) is better than a predetermined position accuracy. It is thus possible, for example in the event of an emergency, to find the location of the communications device more exactly, and define the rescue route more exactly.
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BACKGROUND OF THE INVENTION
This invention relates generally to apparatus for dispensing soluble material into a surrounding body of water. More particularly this invention deals with apparatus that dissolves and dispenses a soluble sanitizing material, preferably calcium hypochlorite, into a body of water, such as a swimming pool utilizing forced circulation.
Chemical feeders, used in previous forced flow or circulation systems, have certain common features. All have typically had a dissolving tank or chamber in which the dissolving of the chemical occurs and a chemical retainer in which the chemical is placed. The dissolving liquid, normally water, is typically fed into the dissolving tank by some control apparatus to ensure the proper amount of chemical dissolved.
Prior equipment, however, normally has suffered from wide fluctuations or variations in the amount of chemical that is dissolved and fed into the water. Most dispensers have utilized a solid chemical that is at least partially immersed in water to effect the dissolution.
Where the chemical is a solid hypochlorite, such as calcium hypochlorite, the solid residue of the chemical has presented either aesthetic or functional problems. When the solid residue has gotten into the forced circulation system, it has resulted in unsightly accumulation on the pool bottom. Build up within the feeder apparatus has resulted in clogging and eventual shutdown of the apparatus. This problem is compounded when larger, commercial pools are treated and larger feeders or dispensers must be used. This clogging also affects the reliability of the feed rate of the chemical into the pools, as well as increasing the frequency of maintenance for these prior feeders.
These problems are solved in the design of the present invention whereby a calcium hypochlorite dispenser operating on the principle of periodic partial immersion with three separate chambers and an improved metering system is provided.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved soluble solid chemical dispenser for a forced circulation system.
It is another object of the present invention to provide an improved calcium hypochlorite dispenser suitable for use in large commercial pools.
It is a feature of the present invention that the calcium hypochlorite dispenser utilizes three separate chambers to achieve uniform and controlled release of the calcium hypochlorite into the pool circulation system.
It is another feature of the present invention that a siphon tube is used to control the amount of water which immerses the solid pool chemical and, therefore, the concentration of the dissolved pool chemical, in the dissolving chamber and the flow of that water into the discharge chamber.
It is yet another feature of the present invention that vertically extendable bellows are connected to the siphon tube to permit the water level in the dissolving tank to be adjusted.
It is still another feature of the present invention that the dispenser utilizes periodic partial immersion to dissolve the chemical in the dissolving chamber.
It is an advantage of the present invention that a solid soluble chemical, such as calcium hypochlorite, is easily dispensed into large commercial sized swimming pools.
It is another advantage of the present invention that clogging of the dispensing apparatus from chemical residue is avoided.
These and other objects, features and advantages are obtained in the three chambered apparatus for dissolving and dispensing solid calcium hypochlorite into a swimming pool wherein the chemical is placed in a chemical chamber that extends down into a dissolving chamber that overlies and is in flow communication with the discharge chamber. The level of water that flows into the dissolving chamber is controlled by a vertically adjustable flow controller that controls the release of treated water from the dissolving chamber into the discharge chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
The objects, features and advantages of the present invention will become apparent upon consideration of the following detailed disclosure of the invention, especially when it is taken in conjunction with the accompanying drawings wherein:
FIG. 1 is a diagrammatic illustration of the pool chemical dispenser of the present invention shown connected via a flow loop to a swimming pool;
FIG. 2 is a side elevational view of the pool chemical dispenser;
FIG. 3 is an enlarged view of the inlet for water that feeds into the siphon tube apparatus to feed water into the dissolving chamber, with a portion cut away to show the flow paths;
FIG. 4 is an enlarged partial side elevational view with a portion of the dispenser cut away and broken off to shown the vertical adjustability of the siphon tube apparatus;
FIG. 4A is an enlarged side elevational view of the settings and the siphon tube apparatus that is vertically adjustable to a plurality of heights.
FIG. 5 is a side elevational view of the chemical dispenser with portions broken away to shown the water level in the dissolving chamber as the siphon tube assembly begins to drain the water from the dissolving chamber into the discharge chamber, as well as showing the chemical chamber extending into the dissolving chamber so that the solid chemical is partially immersed; and
FIG. 6 is a side elevational view of the chemical dispenser with portions broken away to shown the water levels in the dissolving chamber and the discharge chamber after the chemically treated water has started to flow into the flow loop of FIG. 1 enroute to the pool and the water level has dropped below the level of the solid chemical in the chemical chamber.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 discloses the positioning of the pool chemical dispenser, indicated generally by the numeral 10, in the flow loops, indicated generally by the numeral 11 and 12, for the pool 14. Loop 11 connects the dispenser 10 to the pool flow loop 12 by a dispenser flow line 13. Flow line 13 has a filter and housing 15 attached via appropriate fittings on the feed side to receive water from the pool flow loop 12 downstream of forced circulation pump 16. Pool circulation flow line 17 circulates water from the pool 14 and a skimmer feeder (not shown) via forced circulation pump 16 through a pool filter 19 back into the pool. The outlet side of loop 11 connects into loop 12 on the upstream side of pump 16.
As seen generally in FIG. 1 and more specifically in FIG. 2, dispenser 10 has an upper soluble material or chemical chamber 20, an intermediate dissolving chamber 21, inside of which the chemical chamber 20 seats, and a lower discharge chamber 22, inside of which the dissolving chamber seats. The three chambers 20, 21 and 22 are separate, facilitating cleaning and maintenance. The discharge chamber outlet check valve is shown as numeral 44 exiting the side of the discharge chamber 22 and connecting with the dispenser flow line 13.
As is best seen in FIGS. 5 and 6 the chemical chamber 20 has a chemical support grid 28 which is perforated on the bottom to permit water in the dissolving chamber 21 to rise up therethrough into contact with the pool chemical tablets 29 to dissolve the tablets. Chemical chamber 20, when seated in dissolving chamber 21, extends down into chamber 21 so the solid chemical tablets 29 supported by grid 28 are partially immersed as the water fill cycle periodically fills the dissolving chamber 21 to the desired level determined by the water level control means, indicated generally by the numeral 30, in a manner that will be explained hereafter.
Chemical chamber 20 is seen with a removable top 24 to permit easy refill of the tablets 29. Top 24 has a grip handle 25 to facilitate removal. Chamber 20 also has side handle grips 26, only one of which is shown, to permit easy removal of chamber 20 from the dissolving chamber 21.
As is best seen in FIGS. 2 and 4, dissolving chamber 21 has the aforementioned water level control means 30 fastened thereto. This consists of a vertically adjustable control plate 31 and a lock knob 32 that tightens via a conventionally threaded screw to retain the plate 31 at the desired height. FIG. 4 shows control plate 31 in a lowered position in solid lines and in a raised position in phantom lines. Control plate settings 36 are shown in FIG. 4A. Control plate slot 42 permits the control plate to be vertically adjustable.
Siphon assembly, indicated generally by the numeral 33 in FIGS. 3-6, is part of the water level control means 30 that permits the vertical adjustability to be achieved. Bellows 35 are formed from an appropriate flexible material, such as polyethylene, to allow the siphon tube 34 to be raised or lowered. This adjustability is best illustrated in FIG. 4 where the phantom lines show siphon tube 34 and control plate 31 in an elevated position and the solid lines show the same apparatus in a lowered position. Siphon tube 34 is formed from a suitable material, such as polyethylene or other plastic tubing, and is curved or arcuate in shape to permit it to be fastened to control plate 31 and to effectively function as a siphon break, moving up or down with control plate 31. Siphon tube lower section 45 of FIG. 4 is merely raised or lowered in the discharge chamber 22 as the control plate 31 is adjusted.
The curved upper portion of siphon tube 34 functions to control the water level attained in the dissolving chamber 21 from the water flowing in through the flow indicator 39 and the flow indicator feed line 41 to the flow indicator inlet connection 38 via the flow indicator outlet stem tube 40 of FIG. 3. Opening 46 in the inlet connection 38 opposite the outlet stem tube 40 permits the water to flow into dissolving chamber 21 as the water level rises in dissolving chamber 21. The hydraulic pressure within the inlet connection 38 from the water level in dissolving chamber 21 causes the water to rise up through bellows tubing 37 into the bellows 35 section so that the water level in the bellows is the same as the water level in the dissolving chamber 21. Bellows tubing 37 inserts within a stub connection 54 in the flow indicator inlet connection 38 and seats atop O-ring 55 recessed into the inner wall of stub connection 54 to effect a liquid tight seal.
As the water level continues to rise in dissolving chamber 21, the water rises through the bellows 35 section into the upper bellows tubing 37' and then into the siphon tube 34. Once the water level is sufficiently high in dissolving chamber 21 so that the corresponding water level in the siphon tube 34 rises into the curved portion 34' of the siphon tube 34, as seen in FIG. 5, the water starts draining through siphon tube 34 into the discharge chamber 22 at a faster flow rate than the water is flowing in through the flow indicator feed line 41 from the dispenser flow line 13 and the flow controller 48. The siphon tube 34 siphons the chemically treated water from the dissolving chamber 21 back through the flow indicator inlet connection opening 46 of FIG. 3 until the water is drained from the dissolving chamber 21 into the discharge chamber 22. The filling of the discharge chamber 22 and the corresponding lowering of the water level in the dissolving chamber 21 so the pool chemical tablets 29 are no longer immersed in water is shown in FIGS. 5 and 6.
Siphon assembly 33 stops the draining of water through siphon tube 34 from the dissolving chamber 21 to the discharge chamber 22 when air enters the bellows tube 37 in the flow indicator inlet connection because the chemically treated water with the dissolved pool chemical from the tablets 29 has been siphoned off to the lower discharge chamber 22 faster than the inlet flow of water so an air gap is created between the water level in the dissolving chamber and in the flow indicator inlet connection 38 and the bottom of bellows tube 37. This air breaks the siphon and permits the refill of the dissolving chamber 21 to occur to achieve the partial immersion of the pool chemical tablets 29 to recommence the periodic immersion and dissolution cycle. The diameter of the bellows 33 and bellows tube 37 must be wider than the siphon tube 34 to ensure there is a definite air/water break.
Flow controller 48, as seen in FIGS. 1, 5 and 6, provides a constant flow of water into the dispenser 10 via the dispenser flow line 13. This constant flow compensates for pressure fluctuations in the pump 16 of FIG. 1 that result from accumulation of residue that can obstruct flow in loop 12, and hence in dispenser flow loop 11 which can vary by as much as 15-35 pounds per square inch. The constant flow achieves uniform dissolution of the pool chemical tablets 29, resulting in a uniform pool chemical, such as chlorine, feed rate by having uniform cycle times between the filling of dissolving chamber 21 and the draining into discharge chamber 22.
The water level in chamber 22 rises so that the normally closed discharge chamber outlet check value 44 is opened by the action of discharge chamber outlet valve float 49 rising up with the increasing water level to open outlet orifice 50. This permits the chemically treated water to flow out through outlet check valve 44 into the dispenser flow line 13 to be drawn into the downstream side, with respect to circulation pump 16, of the pool circulation flow line 17. Circulation pump 16 then pumps the chemically treated water as shown in FIG. 1 through the filter 19 into the pool 14. Float 49 raises via the pivoting of a pivot arm 51 that pivots downward on the opposing discharge chamber outlet check valve 44 end to drop the valve cap 52 below the outlet orifice 50 to uncover the orifice 50.
As the water drains from the dissolving chamber 21 into the discharge chamber 22 via the siphon assembly 33, the unchecked flow of water into the dispenser 10 via the flow indicator feed line 41 is prevented by a safety overflow assembly, indicated generally by the numeral 56, in FIGS. 5 and 6. Assembly 56 consists of a ball float 58, which is mounted on a float arm 59, that rise upwardly when the water level in discharge chamber 22 reaches the level of the float 58. Float arm 59 extends into the flow controller 48 and connects with a suitable flow interrupter (not shown) which closes off the flow path through flow indicator feed line 41 to stop the flow of water into the dispenser 10. Once sufficient water has exited the discharge chamber 22 via the discharge chamber outlet check valve 44 and dispenser flow line 13, the ball float 58 and float arm 59 drop to reopen the flow path through the flow controller 48.
Flow indicator 39 has a ball 60 inside the clear tubing portion to indicate water flow and the quantity of water flowing into the dispenser 10. When the water flow drops below a predetermined rate indicated, for example, by a flow line on the clear tubing portion, the filter 15 in FIG. 1 requires cleaning. Flow indicator 39 can also have a shutoff valve incorporated into its top in addition to or in lieu of the safety overflow assembly 56 to stop all flow of water into the dispenser 10. The normal flow rate of water out through the siphon assembly 35 is about two times the rate of water entering the dissolving chamber through the flow indicator inlet connection to ensure that the chemically treated water can be siphoned out of the dissolving chamber 21 and a siphon break achieved to stop the flow.
The three chambers 20, 21 and 22 of dispenser 10 are made of any appropriate chlorine resistant material. Preferred is polyethylene, although polyacrylate and polycarbonate are two examples of the many other suitable materials that may be employed. Chemical chamber 20 is tapered so that it is narrower at the top than at the bottom to prevent bridging of the pool chemical tablets 29. This insures a continuous supply of tablets 29 on the chemical support grid 28 for periodic immersion.
In operation, pool chemical tablets 29 are placed in the chemical chamber 20 of dispenser 10 by removal of top 24 after the dispenser 10 has been connected to the pool flow loop 12 of FIG. 1 via the flow loop 11. The control plate 31 is elevated to the desired height and secured in position by tightening the lock knob 32 to control the depth of immersion of the pool chemical tablets 29 in water in the dissolving chamber 21. This setting, selected from the control plate setting 36, also determines the cycle time of the periodic immersions because the siphon tube 34, with its upper curved portion 34', moves with the control plate 31 to determine the water level at which the siphon assembly 33 siphons water from the dissolving chamber 21 into the discharge chamber 22. The amount of time which the pool chemical tablets 29 spend immersed in the water and the quantity of tablets 29 immersed also determine the concentration of the soluble pool chemical in the quantity of water in the dissolving chamber. Flow indicator 39 shows the continued flow of water into the flow indicator inlet connection 38 and, via the inlet connection opening 46, into the dissolving chamber 21.
As the water level in the dissolving chamber 21 rises, the water in the siphon assembly 33 correspondingly rises to the same height up through bellows tube 37, bellows 35, upper bellows tube 37' and siphon tube 34. When the water level inside dissolving chamber 21 and the corresponding level in the siphon assembly 33 reaches the height of the siphon tube curved top portion 34', the water in the siphon assembly flows through the curved top portion 34' and drains out the lower straight section 45 into the discharge chamber 22.
The water in dissolving chamber 21 continues to be siphoned into discharge chamber 22 until an air gap develops between the water level in flow indicator inlet 38 and the lower bellows tube 37. As the water rises in discharge chamber 22 the outlet valve float 49 raises to open the outlet orifice 50 via float pivot arm 50. Once outlet orifice 50 is opened the chemically treated water in the discharge chamber 22 is released into the flow loop 11 where it is drawn into the pool flow loop 12 by the forced circulation of the water by circulation pump 16.
While the preferred structure in which the principles of the present invention have been incorporated is shown and described above, it is to be understood that the invention is not to be limited to the particular details thus presented, but, in fact, widely different means may be employed in the practice of the broader aspects of this invention. The scope of the appended claims is intended to encompass all obvious changes in details, materials, and arrangement of parts which will occur to one of skill in the art upon reading of the disclosure.
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An improved chemical feeder employing periodic partial immersion in a forced circulation system is provided having a soluble chemical chamber, a dissolving chamber into which the soluble chemical chamber extends and a discharge chamber in fluid flow communication with the dissolving chamber to selectively receive chemically treated water from the dissolving chamber and discharge it into a flow loop connected to the forced circulation system.
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BACKGROUND OF THE INVENTION
[0001] This invention relates generally to pumps and more particularly to variable flow rate pumps for hydraulic systems.
[0002] Aircraft gas turbine engines often incorporate various high pressure hydraulic actuators to operate components such as variable geometry exhaust nozzles, vectoring exhaust nozzles, bypass doors, variable stator vanes, and the like.
[0003] Depending on which actuators are being used, the flow requirements vary greatly, and it is desirable to match pumping capacity to the demand. Variable displacement high-pressure piston pumps are therefore commonly used in engine and aircraft hydraulic systems. However, prior art variable displacement piston pumps can be complex, heavy, costly and can lack desired reliability.
BRIEF SUMMARY OF THE INVENTION
[0004] These and other shortcomings of the prior art are addressed by the present invention, which provides a high pressure, variable flow rate pump with low weight and high reliability.
[0005] According to one aspect of the invention, a variable flow pump includes: (a) a housing including an inlet chamber and an outlet chamber interconnected by a main bore; (b) a non-rotating cylinder block with first and second ends disposed in the main bore, the cylinder block including:(i) a central bore disposed in fluid communication with the inlet chamber; (ii) a plurality of cylinder bores arrayed around the central bore; (iii) a plurality of first feed passages interconnecting the inlet chamber and the cylinder bores, the first feed passages defining a bypass flowpath between the cylinder bores; and (iv) at least one check valve disposed at the second end which permits fluid flow from the cylinder bores to the discharge chamber but prevents flow in the opposite direction; (d) a plurality of pistons disposed in the bores; (e) a shaft mechanically coupled to the pistons so as to cause the pistons to reciprocate through an axial pump stroke between predetermined fill and discharge positions, when the shaft is rotated; and (f) a mechanism coupled to the cylinder block which is adapted to selectively axially position the cylinder block within the housing, so as to vary the size of the bypass flowpath.
[0006] According to another aspect of the invention, a method of operating a variable flow pump includes: (a) receiving fluid into an inlet chamber of a housing of the pump, wherein the pump includes an inlet chamber and an outlet chamber interconnected by a main bore; and (b) using a piston which reciprocates through an axial pump stroke between predetermined fill and discharge positions: (i) drawing fluid from the inlet chamber into a cylinder bore in a non-rotating cylinder block with first and second ends disposed in the main bore; (ii) discharging fluid through the cylinder bore; and (iii) during discharge, selectively bypassing a portion of the fluid from the cylinder bore through a first feed passage into the inlet chamber, the proportion of bypass being controlled by modulating the axial position of the cylinder block within the housing.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The invention may be best understood by reference to the following description taken in conjunction with the accompanying drawing figures in which:
[0008] FIG. 1 is a schematic cross-sectional view of a pump constructed according to an aspect of the present invention;
[0009] FIG. 2 is another view of the pump of FIG. 1 ;
[0010] FIG. 3 is another view of the pump of FIG. 1 ;
[0011] FIG. 4 is a view taken along lines 4 - 4 of FIG. 1 ; and
[0012] FIG. 5 is a view taken along lines 5 - 5 of FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
[0013] Referring to the drawings wherein identical reference numerals denote the same elements throughout the various views, FIG. 1 depicts a variable displacement pump 10 . The major components of the pump 10 are a housing 12 , cylinder block 14 , shaft 16 , wobble plate 18 , pistons 20 , and flow modulating assembly 22 .
[0014] The housing 12 includes a main bore 24 . An inlet chamber 26 is disposed at one end of the main bore 24 and a discharge chamber 28 is disposed at the opposite end. An inlet 30 connects to the inlet chamber 26 , and an outlet 32 connects to the discharge chamber 28 .
[0015] The cylinder block 14 is received in the main bore 24 . It is free to move axially, between a maximum flow position (seen in FIG. 3 ) and a minimum flow position (seen in FIG. 1 ). The cylinder block 14 is generally cylindrical and has a first end 34 and a second end 36 . A central bore 38 passes down the rotational axis of the cylinder block 14 . It is open at the first end to receive the shaft 16 , and is closed at the second end 36 . A plurality of cylinder bores 40 are arrayed around the central bore 38 . A set of first feed passages 42 (i.e. slots, holes, or the like) are arrayed around the wall 44 separating the central bore 38 and the cylinder bores 40 . A set of second feed passages 46 are located axially downstream of the first feed passages 42 . The second end 36 of the cylinder block 14 carries discharge valves 48 which prevent backflow from the discharge chamber 28 back into the cylinder bores 40 . In this particular example, as seen most clearly in FIG. 5 , the discharge valves 48 are reed valves which are part of a single valve plate 50 attached to the second end 36 of the cylinder block 14 . Other types of check valves could be substituted for this purpose. Leakage between the housing 12 and the cylinder block 14 is minimized by one or more seals 52 . Preferably the seals 52 are a low-friction type. In the illustrated example, the seals 52 are commercially available “O”-ring energized seals with low-friction caps made from a material such as polytetrafluoroethylene (PTFE), graphite, or the like.
[0016] The shaft 16 passes through appropriate bearings and seals 54 in the housing 12 . A first end of the shaft 16 extends outside the housing 12 and incorporates one or more mechanical features (not shown) such as a keyway, splines, or a driven gear, allowing the shaft to be connected to a driving element.
[0017] The opposite end of the shaft 16 is formed into an enlarged plug 55 having a cylindrical outer surface 56 which fits closely in the central bore 38 . A bleed port 57 is provided in the shaft 16 which lets working fluid pass freely between the inlet chamber 26 and the interior of the central bore 38 . This allows the cylinder block 14 to translate axially relative to the shaft 16 without causing excessive loads or hydraulic lock. A rotating port 58 is incorporated near the second end to pass working fluid from the inlet chamber 26 to the second feed passages 46 . As seen in FIG. 4 , the rotating port 58 may take the form of a groove which extends halfway around the circumference of the plug 55 . The rotating port 58 is positioned or “clocked” such that when a piston 20 is in the “inlet” stroke, (the upper piston 20 in FIG. 1 ), the rotating port 58 is open to the associated cylinder bore 40 , but when a piston 20 is in the “discharge” stroke, (the lower piston 20 in FIG. 1 ), the corresponding cylinder bore 40 is closed off.
[0018] As seen in FIG. 1 , the wobble plate 18 is mounted to the shaft 16 and is positioned in the inlet chamber 26 . The wobble plate 18 is coupled to the pistons 20 in a manner that permits rotation of the shaft 16 to be converted into reciprocating axial motion of the pistons 20 . In the illustrated example, the wobble plate 18 has a low-friction working face 60 , which may be accomplished through polishing, application of anti-friction coatings, or the like. The working face 60 is disposed at a non-perpendicular angle “A” to the rotational axis of the shaft 16 . Mounted on the working face 60 are annular flanges 62 that define an annular channel 64 . A plurality of slippers 66 are received in the channel 64 and are coupled to connecting rods 68 , for example through the illustrated ball joints 70 . Each of the connecting rods 68 is in turn coupled to one of the generally cylindrical pistons 20 . The pistons 20 can move axially but are restrained from any lateral movement by the cylinder block 14 . As the wobble plate 18 is rotated by the shaft 16 , the individual slippers 66 will be alternately pushed or pulled, in turn pushing or pulling the corresponding connecting rod 68 and piston 20 . At any particular time in the cycle, one of the pistons 20 will be at a fully extended position (to the right in FIG. 1 ). The diametrically opposite piston 20 will be at a fully retracted position (to the left in FIG. 1 ), and the remaining pistons 20 will be at intermediate positions. The wobble plate angle A may be selected to provide the desired magnitude of axial piston stroke. The number and size of the pistons 20 as well as the shaft speed may be varied to suit a particular application as well.
[0019] Means are provided for selectively moving the cylinder block 14 to a desired axial position relative to the housing 12 . Any type of actuator capable of moving the cylinder block 14 (e.g. electrical, hydraulic) may be used. In the illustrated example, the cylinder block 14 is moved by an electrohydraulic servo valve (EHSV) 72 of a known type in which a small pilot valve (not illustrated) is used to port working fluid pressure to either side of a primary cylinder (shown schematically at 74 ). As shown, discharge pressure may be ported to a pressure regulator 76 which in turn feeds regulated fluid pressure to the EHSV 72 through a line 78 . The pressure drop across the EHSV 72 is thus nearly constant over a wide range of pump output pressures, which simplifies control programming. A controller 80 including one or more processors, such as a programmable logic controller (PLC) or computer, is coupled to the EHSV 72 . The controller 80 responds to a flow demand signal and in turn drives the EHSV 72 to an appropriate position. A suitable transducer (not shown), such as a linear variable differential transformer (LVDT), may be used to provide cylinder block axial position feedback information to the controller 80 .
[0020] The pump 10 operates as follows. Working fluid enters the inlet 30 and floods the inlet chamber 26 volume on the left side of the pump 10 . The fluid is at a relatively low inlet pressure, which may be supplied by a suitable boost pump of a known type (not shown). Meanwhile the shaft 16 is rotating, causing the pistons 20 to reciprocate as described above. When a piston 20 is in the retracted or fill position, (the upper piston 20 in FIG. 1 ), the associated cylinder bore 40 is flooded with working fluid through the rotating port 58 , and the first and second feed passages 42 and 46 . During the discharge stroke (the lower piston 20 in FIG. 1 ), the rotating port 58 closes off the second feed passages 46 as described above. As the piston 20 begins its discharge stroke the pumped fluid is initially bypassed back to the inlet chamber 26 through the pressure through the first feed passages 42 . When the piston 20 reaches the end of the first feed passage 42 , the remaining stroke pumps fluid through the discharge valve 48 to the discharge chamber 28 and subsequently through the outlet 32 .
[0021] Discharge flow is varied by altering the percentage of piston stroke delivering fluid to the discharge chamber 28 versus bypass flow back to the inlet chamber 26 . This is achieved by modulation of the axial position of the cylinder block 14 . FIG. 1 illustrates a minimum flow position of the cylinder block 14 , where the cylinder block 14 is shifted towards the discharge chamber 28 . This position exposes the first feed passages 42 for the maximum amount of the piston stroke. FIG. 2 illustrates an intermediate flow position. Relative to FIG. 1 , the cylinder block 14 is shifted towards the inlet chamber 26 . This causes the first feed passages 42 to be cut off sooner in the piston stroke. FIG. 3 illustrates a maximum flow position. In this position, the cylinder block 14 is shifted as far towards the inlet chamber 26 as possible. In this position there is no bypass flow through the first feed passages 42 .
[0022] The pump may also include a balance piston 82 . In operation, discharge pressure is ported to the balance piston 82 through a line 84 . This pressure tends to drive the cylinder block 14 towards the right, in opposition to the force applied by discharge pressure on the second end of the cylinder block 14 . The area of the balance piston 82 may be selected such that the net axial force on the cylinder block 14 is zero or very small, thereby reducing bearing loads. With the balance piston 82 , the EHSV 72 need only have enough capacity to overcome seal friction and allows the EHSV 72 to be much smaller than it would have to be otherwise.
[0023] If desired, the pump 10 can include a pressure relief valve 86 . If the discharge pressure exceeds the relief valve's set point, flow is bypassed to the inlet chamber 26 .
[0024] The foregoing has described a variable flow pump. While specific embodiments of the present invention have been described, it will be apparent to those skilled in the art that various modifications thereto can be made without departing from the spirit and scope of the invention. Accordingly, the foregoing description of the preferred embodiment of the invention and the best mode for practicing the invention are provided for the purpose of illustration only and not for the purpose of limitation.
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A variable flow pump includes: a housing with inlet and outlet chambers interconnected by a main bore and a non-rotating cylinder block positioned in the main bore. The cylinder block includes: a central bore communicating with the inlet chamber; cylinder bores arrayed around the central bore; first feed passages interconnecting the inlet chamber and the cylinder bores, defining a bypass flowpath between the cylinder bores; and at least one discharge valve disposed at the second end which permits fluid flow from the cylinder bores to the discharge chamber but prevents opposite flow; Pistons are disposed in the bores. A shaft is coupled to the pistons so as to cause them to reciprocate through an axial pump stroke when the shaft is rotated. A mechanism is coupled to the cylinder block which modulates the axial position of the cylinder block within the housing, varying the size of the bypass flowpath.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a National entry of PCT/CA2007/000198 filed Feb. 12, 2007, in which the United States of America was designated and elected, and which remains pending in the International phase until Sep. 13, 2008, which application in turn claims priority from U.S. Provisional application Ser. No. 60/781,385 filed Mar. 13, 2006.
The application claims priority under 35 U.S.C. 119(e) from U.S. Provisional application Ser. No. 60/781,385 filed Mar. 13, 2006.
TECHNICAL FIELD
This invention relates to a method for bleaching a lignocellulosic material, and more particularly, to a method for improving the performance of chlorine dioxide in the process of bleaching lignocellulosic pulp.
BACKGROUND ART
The removal of lignin in lignocellulosic materials such as chemical pulp is accomplished by a multi-stage application of bleaching chemicals. Chlorine dioxide is the chemical of choice because it reacts readily and selectively with lignin and does not react to any significant extent with carbohydrate. A typical bleaching sequence uses a chlorine dioxide delignification stage (notated as D 0 ), an alkaline extraction stage in which oxygen gas and peroxide are commonly added (notated as Eop), and a final brightening procedure which can comprise one chlorine dioxide stage (notated as D) or two chlorine dioxide stages (notated as D 1 and D 2 , respectively) with or without an intermediate extraction stage.
A final chlorine dioxide bleaching stage, such as D or D 2 , is typically run at a temperature between 55 to 85° C. with a retention time between 2 and 4 hours and a consistency between 8 and 15%. The pH is typically adjusted with sodium hydroxide or sulphuric acid before the chlorine dioxide to provide a final pH of between 3.5 and 4.0.
Prior art shows that the maximum brightness development is achieved by keeping the pH during the final brightening stage very close to neutral (5.0 to 7.0). It has been demonstrated in the laboratory that, by using soluble buffers such as potassium dihydrogen phosphate, maximum brightness is achieved at a pH between 5.0 and 6.5 [1]. Canadian Patent No. 756,967 discloses a process for neutral chlorine dioxide bleaching wherein neutral conditions are maintained by the addition of carbonates, oxides of alkaline earth materials, or bicarbonates of alkali or alkaline earth metals which are of sufficiently limited solubility [2]. Neither of these processes are practised commercially. The soluble buffers such as potassium dihydrogen phosphate are too expensive for industrial application while the handling of sparingly soluble buffers such as sodium bicarbonate is difficult. For these reasons present industrial practice is to adjust pH at the beginning of the stage with either a soluble alkali or acid to provide a final pH of between 3.5 and 4.0, which has been reported as the optimal end pH under unbuffered conditions [3,4].
DISCLOSURE OF THE INVENTION
It is an object of this invention to provide an improved process for delignification of a lignocellulosic pulp.
It is a further object of this invention to provide a process for delignification of a lignocellulosic pulp.
It is a specific object of the present invention to provide an improvement to a final chlorine dioxide bleaching stage such as D or D 2 , in the delignification of a lignocellulosic pulp, by increasing the brightness before and/or after the application of fluorescent whitening agent (FWA) or optical brightening agent (OPA) with the same charge of chlorine dioxide and FWA or OPA.
It is another specific object of this invention to provide an improvement to a final chlorine dioxide bleaching stage such as D or D 2 , in the delignification of a lignocellulosic pulp, by maintaining the brightness before and/or after the application of fluorescent whitening agent (FWA) or optical brightening agent (OPA) with a smaller chlorine dioxide charge in the final stage or in previous stages and/or a smaller charge of FWA or OPA.
In one aspect of the invention, there is provided in a process for delignification of a lignocellulosic pulp in an aqueous suspension in which delignification is carried out with chlorine dioxide at least in a final bleaching stage, the improvement wherein said final bleaching stage is carried out at a pH buffered in a neutral region, the buffered pH being established by in situ generation of bicarbonate in said pulp suspension from an alkaline agent and carbon dioxide in the suspension.
In another aspect of the invention, there is provided a process for delignification of a lignocellulosic pulp in an aqueous suspension comprising the steps of:
a) bleaching the pulp in said suspension, in which a final bleaching is carried out with chlorine dioxide at a buffered pH in a neutral region, wherein the buffered pH is established by in situ generation of bicarbonate in said pulp suspension, from an alkaline agent and carbon dioxide in the suspension, and b) brightening the bleached pulp from step a) with a fluorescent whitening agent or an optical brightening agent.
DETAILED DESCRIPTION OF THE INVENTION
The process of the invention enhances the effectiveness of chlorine dioxide bleaching of lignocellulosic material and is a process in which the final chlorine dioxide bleaching stage is maintained under a near-neutral pH by the in-situ formation of a sparingly soluble buffer by applying an alkaline agent and carbon dioxide.
The invention relates to the in-situ formation of a sparingly soluble buffer and the adjustment of the pH to near-neutral. The buffer can be formed by the application of an alkaline solution followed by the application of carbon dioxide which, in contact with the alkaline solution, forms a bicarbonate buffer and brings the pH to near neutral; or the application, to an already alkaline pulp, of carbon dioxide which, in contact with the alkaline pulp, forms a bicarbonate buffer and brings the pH to near neutral.
In the present invention, the near-neutral pH condition is maintained by the addition of carbon dioxide to an alkaline slurry of the pulp to be bleached in a final chlorine dioxide stage. Under some industrial operating conditions the pulp slurry may already be in an alkaline form, for example, after an alkaline extraction stage. Under other conditions the pulp may need to be first adjusted to an alkaline pH. The amount of alkalinity present in the pulp must be adequate to produce enough bicarbonate when carbon dioxide is added, to maintain the near-neutral pH during the addition of the acidic chlorine dioxide and the acid-generating bleaching stage. Alkali addition points can be the washer showers, the washer repulper, the steam mixer and the chemical mixer. Carbon dioxide addition points can be the steam and chemical mixers.
The preferred method of addition is injection of carbon dioxide gas into the pulp slurry. The carbon dioxide may, however, also be added in liquid or solid form. The initial pH, after carbon dioxide addition and before chlorine dioxide addition, is generally in the range between 7 and 10 and the final pH is suitably 4.5 to 7 and preferably in the range between 5 and 6.
The lignocellulosic materials used in the method of the present invention can be a wood and/or non-wood derived lignocellulosic material and can be introduced as chips, wafers, slivers, or pulps which are treated with other known bleaching agents before being subjected to the final chlorine dioxide bleaching. For example, typical bleaching stages applied to a pulp before a final chlorine dioxide bleaching stage can be another chlorine dioxide stage, an extraction, oxygen delignification, ozone, peroxide, peracetic acid, chelation, acid hydrolysis, or enzyme treatment, applied as a single stage or as multi-stages, with or without washing between the stages.
Typically the delignification process is a multi-stage bleaching, and the carbon dioxide is added to the pulp suspension immediately prior to the final chlorine dioxide bleaching stage.
Typically the multi-stage bleaching has a sequence selected from:
D 0 E x D, D 0 E x D 1 D 2 , D o E x D 1 nD 2 and D 0 E x D 1 E D 2 ,
in which E x is E, E 0 , E p or E op where n indicates addition of alkali at the end of the D 1 stage.
The alkaline agent which reacts with carbon dioxide to generate bicarbonate in situ in the pulp suspension is suitably a hydroxide of an alkali metal or an alkaline earth metal. Suitable hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide and magnesium hydroxide.
The fluorescent whitening agent or optical brightening agent added to the pulp recovered from the process of the invention may be added directly to the pulp or to a paper formed from the pulp. A full description of these types of agent is given in Reference 5, the teachings of which are incorporated herein by reference, but typically the agents used in pulp and paper applications are based on stilbene-triazine or biphenyl structures. Suitable agents are bistriazinyl derivatives of 4,4′-diaminostilbene-2,2′-disulfonic acid; 2-(stilbene-4-yl)naphthotriazoles; 2-(4-phenylstilbene-4-yl)benzoazoles; bis(azol-2-yl)stilbenes; bis(styryl)benzenes, bis(styryl)biphenyls; bis(benzimidazol-2-yl)s; 2-(benzofuran-2-yl)benzimidazoles; coumarins, carbostyrils; and alkoxy-naphthalimides.
The process of the invention improves the brightness of the pulp and also provides an improvement in the response of the bleached pulp to subsequently applied fluorescent whitening agent or optical brightening agent.
Thus, in one advantageous embodiment, the bleaching in step a) is carried out with a reduced charge of chlorine dioxide while achieving a brightness in the pulp recovered from step b) comparable to that when the delignification is carried out with a full charge of chlorine dioxide, in the absence of the in situ generation of the bicarbonate.
In another advantageous embodiment, the brightening in step b) is carried out with a reduced charge of the whitening agent or brightening agent, while achieving a brightness in the pulp recovered from step b) comparable to that when the delignification is carried out with a full charge of the whitening agent or brightening agent.
In still another advantageous embodiment, the process of the invention includes a step of recovering a pulp from step b) having a brightness higher than that for a comparable process in the absence of the in situ generation of the bicarbonate.
The chlorine dioxide solution used in the method of the present invention can be generated using known processes and may or may not contain chlorine or other chlorine species. The lignocellulosic material is placed in a vessel or container, to which is added a solution containing chlorine dioxide. The bleaching reaction is conducted at a temperature within the range from about 40° C. to about 95° C., at a consistency from 2 to 20%. The amount of chlorine dioxide added to the stage, based on oven-dry lignocellulosic material, can range from 0.5 to 20 kg/ton.
In a preferred embodiment of the invention, the conditions in the final chlorine dioxide stage are a temperature of 70° C., a consistency of 10%, and a chlorine dioxide charge of between 1 and 2 kg/ton based on oven-dry lignocellulosic material.
In this specification, a pH in a neutral region is understood to be one close to or at neutral pH, more especially 4.5 to 7 and preferably 5 to 6.
EXAMPLES
In order to disclose more clearly the nature of the present invention, the following examples illustrate the invention.
Example 1
A hardwood kraft pulp oxygen-delignified and partially bleached in a mill with a D 0 Eop sequence was thoroughly washed in the laboratory and bleached with a final chlorine dioxide stage. D 0 represents a chlorine dioxide delignification stage, while Eop represents an alkaline extraction stage fortified with oxygen and peroxide. The kappa number of the D 0 Eop pulp was 2.0.
The final chlorine dioxide bleaching stage (D) was carried out by placing the pulp in a vessel, and mixing appropriately heated water into the pulp and adjusting the pH to a predetermined value using sodium hydroxide (NaOH) or carbon dioxide if required, followed immediately by a rapid addition of chlorine dioxide solution. The charge of chlorine dioxide added to the pulp slurry was set at 1.70 kg per ton of oven-dry pulp. The pulp consistency was 12.0%, the reaction temperature was 70° C., and the reaction time was 97 minutes. After the reaction, the pulp was thoroughly washed.
TABLE 1
Experiment number
1
2
3
4
NaOH added
—
0.5
0.14
0.28
kg/ton on o.d. pulp
basis
CO 2 added
—
—
0.14
0.28
kg/ton on o.d. pulp
basis
H 2 SO 4 added
2.5
—
—
—
kg/ton on o.d. pulp
basis
pH just before ClO 2
3.5
11.1
7.9
9.4
addition
Final pH
3.4
6.0
5.3
6.0
ISO brightness, %
91.4
91.6
91.9
91.9
It is readily evident from the results in Table I, that there is a brightness advantage over conventional operation (Experiment 1) that is obtained by using the application of an alkali and carbon dioxide (Experiments 3 and 4) to buffer the final brightening stage. It is also evident from Table I that achieving a final pH in the targeted range without buffering (Experiment 2) does not give the brightness increase that is possible from the process described in this application. The enhanced effectiveness of chlorine dioxide bleaching through achieving and maintaining a near-neutral pH is shown by the higher ISO brightness obtained (91.9%, Experiment Number 3 and 4) than that obtained in the control experiment (91.4%, Experiment Number 1).
Example 2
An oxygen-delignified hardwood kraft pulp with a kappa number 7.6 was bleached using a D 0 EopD sequence.
The D 0 and D stages used the procedures employed in Example 1 but the charges of chlorine dioxide in the D 0 stage was decreased substantially when near-neutral conditions were used. The charges of chlorine dioxide in the D 0 EopD sequence were as follows: 0.62% or 0.85% in the D 0 stage for near-neutral or conventional bleaching respectively and 0.17% in the D stage. Other reaction conditions for the D 0 stage were: consistency 10%, reaction time 54 minutes, reaction temperature 60° C. Other reaction conditions for the D stage were: consistency 12%, reaction time 97 minutes, reaction temperature 70° C. The D stage was carried out with and without adding using carbon dioxide.
The extraction stage (Eop) was carried out at 10% consistency in a laboratory pressurized peg mixer maintained at 0.14 MPa oxygen pressure for the first 10 minutes of the reaction, and at atmospheric pressure for 50 minutes. The reaction temperature was maintained at 75° C. and the charge of NaOH and peroxide was 0.64% and 0.33% based on the weight of oven-dried pulp, respectively.
The pulp was thoroughly washed after each bleaching stage.
Handsheet samples of the D 0 EopD bleached pulps were also prepared for evaluating their responses toward fluorescent whitening agents (FWA) or optical brightening agents (OPA). A volume of Tinopah HW solution (0.5% of deionised water) was applied to the handsheet sample with a syringe and the sample was then dried and brightness measured.
It is readily evident from an examination of the results in Table II, that compared to the conventional D stage (Experiment 6), the present invention of maintaining a near-neutral pH in the D stage by using carbon dioxide and a base (Experiment 5) still gives a higher final brightness (91.7 versus 91.4) even when the amount of chlorine dioxide used in the D 0 stage has been decreased by 27%. It is also readily evident from the data in the last 2 rows of Table II that it also provides an improvement to the response of the final bleached pulps toward the application of a fluorescent whitening agent.
TABLE II
Experiment number
(D 0 EopD sequence)
5
6
Chlorine dioxide added in D 0
6.2
8.5
kg/ton on o.d. pulp basis
Kappa number after D 0 Eop
3.0
2.2
Chlorine dioxide added in D
1.7
1.7
kg/ton on o.d. pulp basis
H 2 SO 4 added in D
—
0.5
kg/ton on o.d. pulp basis
NaOH added in D
0.28
—
kg/ton on o.d. pulp basis
CO 2 added in D
0.38
—
kg/ton on o.d. pulp basis
Final pH in D
5.5
3.2
ISO brightness after D 0 EopD, %
91.7
91.4
Unit of brightness gain (ISO, %)
5.6
4.2
after FWA application with a
charge of Tinopal HW
of 0.2% w/w (based on o.d.)
Unit of brightness gain (ISO, %)
6.6
5.9
after FWA application with a
charge of Tinopal HW
of 1.0% w/w (based on o.d.)
REFERENCES
1. Rapson, W. H., Tappi J, 39(5):284, 1956.
2. Sepall, O., Canadian Patent No. 756, 967, 1967.
3. Rapson, W. H. and Anderson, C. B., CPPA Trans. Tech Sect, 3(2):TR52, 1977.
4. Reeve, D. W., in Pulp Bleaching—Principle and Practice , (C. W. Dence and D. W. Reeve, Eds.), TAPPI Press, Atlanta, 1996, pp. 379-394.
5. Kirk-Othmer 4 th Edition, “Fluorescent Whitening Agents”. Vol. 11, p. 227.
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Final chlorine dioxide bleaching of lignocellulosic materials is most effective at a near-neutral pH but present industrial practice typically targets a final pH of between 3.5 and 4.0 because of the difficulty in achieving and maintaining near-neutral pH cost effectively. The in situ formation of bicarbonate before the addition of chlorine dioxide provides a way of maintaining the required near-neutral pH. Near-neutral final chlorine dioxide bleaching also produces a bleached pulp that is in a state that responds more effectively to fluorescent whitening or optical brightening agents.
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CROSS REFERENCE TO RELATED APPLICATION
This application claims the benefit of applicant's Provisional Application Serial No. 60/153,777, filed Sep. 14, 1999.
FIELD OF THE INVENTION
This invention relates to grinding machines and more particularly to high-precision grinders using CNC controls.
BACKGROUND OF THE INVENTION
Definitions: “CNC” refers to computer numerical control systems as employed for operation of machine tools.
“Chucker” refers to a workhead for a grinding or turning machine having a clamping device or chuck capable of holding only a part short enough not to require a tailstock at the opposite end of the part during grinding or turning. No part support other than the chuck is provided at the driven end of the part.
Grinding machines using a single workhead and a CNC control system have been employed previously for high-precision applications. Prior grinders of this type have generally coupled a CNC control system to a grinding wheel spindle for movement along an in-feed axis, which brings the wheel into contact with a supported workpiece being held in position on a single workhead by a chuck or other clamping device. The workhead in this approach is not fed into the wheel for grinding, but is held in place once adjusted.
It would be advantageous to provide improved CNC chucker grinders capable of providing increased production rates without sacrificing any of the high degree of precision obtained.
SUMMARY OF THE INVENTION
The present invention is directed to a grinding machine comprising a grinding wheel and a pair of workheads mounted on supporting structure enabling independent movement of the workheads toward and away from the grinding wheel, with operation of the workheads and chucks attached thereto being carried out under separate and independent CNC controls.
Supporting structure for the workheads includes a horizontally extending base having a generally flat bed surface carrying laterally extending linear rails or V and flat linear motion guides adapted for receiving mating elements placed underneath a pair of aligned workslides. Movement of the workslides in a lateral direction, generally parallel to the grinding wheel spindle, may be carried out by linear ball screws driven by servo motors. The ball screws typically are rotatably mounted in bearing blocks or housing and are connected to ball nuts which are fixedly attached to the workslides.
Each of the workslides carries a cross slide and connecting elements necessary for support and movement of an upper platform of the cross slide in a direction perpendicular to the wheel spindle. The platform rests on a lower block portion of the workslide, with linear rails attached to the lower portion and mating elements provided underneath the upper platform. Movement of the cross slide is enabled by use of a ball screw, bearing blocks or housings and a driving servo motor in a manner. similar to those used for work slide movement.
A spindle case aligned for driving a workhead chuck is provided of the upper platform of each cross slide. A spindle carried in the case extends from the innermost side of the. case and has a spindle nose which serves as a plate for attachment of a rotatable chuck. The chuck is driven by a servo motor placed alongside and propelling a belt engaged with pulleys on the motor and spindle.
The machine may thus provide for controlled linear movement of both workheads and a wheelhead along five or more linear axes and for controlled rotary movement of each of two chucks around rotary axes. Each of the movements involved is controlled by the CNC System of the machine. In order to obtain high precision between workpieces being simultaneously ground-while supported on dual workheads, each of the workheads is controlled independent. of the other, but in coordination with control of the grinding wheel.
The CNC control system may make use of computer software programmed to include parameters such as extent and timing of movements, grinding speeds, starting and final dimensions of workpieces and the like. Additional data entries and modifications may be inserted by a keyboard operater using conventional techniques. Information derived from in-process gauges may also be fed into the control system to provide precision timing of grinding shutoffs. By using independent CNC controls for the two workheads, separate workpieces may be ground to meet the same or different requirements. Grinding of one workpiece may be completed and terminated by retracting its workhead while the other is still being ground.
Grinding machines of this invention provide a high degree of precision such as 20 millionths of an inch. This result is enabled by various factors, including use of servo motors having a resolver or encoder capable of providing a high number of incremental counts per revolution such as 4,000,000. This level of precision would not be available if a single CNC control were used in propelling a grinding wheel against a pair of separately supported workpieces.
An increased production rate, twice the rate for single workhead machines once set-up is performed, may be obtained by this invention without any compromise of precision.
It is, therefore, an object of this invention to provide a high-precision grinding machine capable of operating at an increased production rate.
Another object is to provide a grinding machine wherein a pair of independently controlled workpieces may be ground simultaneously on a single grinding wheel.
Other objects and advantages of the invention will be apparent from the following detailed description and claims appended hereto.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an overall isometric view of a grinding machine embodying the invention.
FIG. 2 is an isometric view showing underlying support structure for the movable workheads and a wheelhead of the machine of FIG. 1 .
FIG. 3 is an isometric view showing movable support structure for a cross slide of the grinding machine.
FIG. 4 is an end view of a workhead assembly taken from an outside location at a corner of the machine.
FIG. 5 is a schematic view showing operation of a control system for the machine.
FIG. 6 is a schematic side view of an embodiment wherein dual grinding wheels for internal grinding are provided.
FIG. 7 is a schematic top view of the machine of FIG. 6 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1 of the drawings, there is shown a grinding machine 10 on which workpieces supported on dual workheads, 12 , 13 may be ground by being brought into contact with a grinding wheel 14 carried on spindle 16 . Right workhead 13 , designated only by dotted lines, is a mirror image of left workhead 12 , and it is to be understood that all description of the left workhead applies equally to the right one.
Workhead 12 is supported on carriage assembly 18 structured to provide linear movements in X and Y directions as required for positioning of workpieces, while wheelhead assembly 20 provides for movement only in a direction perpendicular to the wheel spindle.
Wheelhead assembly 20 has a fixed block 22 secured to horizontal base 24 , with a V and flat way 25 , including a V groove 26 defined adjacent one edge and a flat surface 28 defined along the other edge. A channel 30 of rectangular cross section, in which bearing blocks 32 are located, extends along the length of the block.
Wheel slide 34 is arranged for linear movement-along block 22 with movement being guided by a V-shaped projection 35 extending along the bottom of the slide on one side and conforming to V groove 26 . A flat surface 36 is provided along the other side of the slide in position to come in to sliding contact with flat surface 28 defined along the other edge. A channel 30 of rectangular cross section, in which bearing blocks 32 are located, extends along the length of the block.
Wheel slide 34 is arranged for linear movement along block 22 with movement being guided by a V-shaped projection 35 extending along the bottom of the slide on one side and conforming to V-groove 26 . A flat surface 36 is provided along the other side of the slide in position to come into sliding contact with flat surface 28 along the top of block 22 .
Servo motor 38 , located at the outside end of wheelhead block 22 , drives a ball screw 40 (FIG. 2 ), which propels a ball nut 42 connected to wheelslide 34 , thus moving the grinding wheel inward toward the workheads and outward away from them.
In operation, movement of the wheelslide toward and away from the workheads may be controlled by the CNC system in accordance with programmed or keyboard-inputted instructions. For high-precision applications inward movement at startup of grind would be limited to bringing the wheelhead into a desired starting position and holding such position fixed while independently controlled movements of the dual workheads provide movements during grinding.
Workhead carriage assembly 18 has a workslide 44 with a bottom structure adapted to fit over linear rails 46 disposed on base 24 and aligned parallel to spindle 16 of the wheelhead. Movement of the workslide in a direction parallel to the spindle is provided by ball screw 48 (FIG. 2) driven by servo motor 50 . The balls crew is mounted on bearing blocks 52 , 54 fixed to the base, and ball nut 56 , bolted to the slide, propels the slide upon turning of the ball screw. Bearing packs 58 include bearings which come into moving contact with sides of linear rails 46 .
Cross slide 60 , which enables controlled movement perpendicular to the workslide linear rails and to the grinding wheel spindle, is located on top of workslide 44 . Cross slide 60 has a base plate 62 slidably mounted on top of supporting plate 64 (FIG. 3) attached to the work slide. Linear rails 66 , 68 connected to base plate 64 provide a track for movement of the cross slide. In a manner similar to structure of the workslide, movement of the cross slide is produced by a ball screw 70 driven by a servo motor 72 , with a movable ball nut 73 being connected to base plate 62 . Bearing packs 74 (FIG. 4) disposed along the lengths of linear rails 66 , 68 to facilitate movement of the cross slide.
A spindle case 76 , carrying a spindle 78 for operation of a rotating chuck 80 , is connected to plate 62 with a driving motor 82 placed alongside. Chuck 80 is mounted on spindle nose 84 and includes clamping jaws 86 .
As shown in FIG. 4, chuck 80 is powered for rotation by motor 82 connected to the chuck through belt 88 which engages pulleys 90 , 92 . The workhead may also carry a gauge 94 in position to obtain a real-time indication of completion of programmed grinding. The gauge shown in FIG. 1 has cantilevered sensors 96 , 98 , one provided for outer diameter monitoring of a cylindrical workpiece and the other monitoring other parameters, as required. The sensor may provide a signal to the control system which initiates immediate shutdown.
In operation of the machine, workpieces to be ground are secured in position by jaws or other holders of the at chucks and are placed in proper alignment for coming into contact with the grinding wheel upon being moved. Movements of the workheads which support the workpieces are controlled by a CNC system which includes dual workhead controls, each one independent of the other.
FIG. 5 schematically shows a CNC control system for implementing the invention. Inputs to the system may come from prepared computer programs, keyboard-inputted modifications to the programs or gauges or other sensors monitoring the grinding process. Data processing outputs are converted to signals actuating the dual workheads, chucks and wheelhead. The wheelhead is programmed to provide movement of the grinding wheel along a single input axis to a desired location, after which movement of the wheelhead ceases, and relative movement of wheel and workpieces is obtained only by workhead movements. Inputs to each of the workheads provides signals implementing programmed movements along X and Y axis through movements of the work slide and cross slide. Movements of workpiece supporting chucks around programmed rotary axes are also implemented.
A typical sequence of events in operation of the machine is illustrated as follows:
1. Part is loaded into work holding device in both workheads.
2. Cycle start is actuated.
3. Grinding wheel axis (main process) initiates command for workheads to run their respective programs. Left workhead and its related axis is designated as process 1 and the right workhead (and related axis) is designated as process 2 .
4. Grinding Wheel axis moves into grind position, which is designated by its program.
5. Left and right workheads position themselves into their respective grind positions.
6. Left and right workheads begin running the axis cross feeds at the programmed feed rate to the desired position to achieve final part size:
a. should either process ( 1 or 2 ) achieve size first, that respective workhead is retracted from the grinding wheel and commanded to return to its “home” or programmed load position
b. the remaining process continues program execution until final size is reached, irrespective of the other process
c. when process in b. achieves size, the workhead retracts from grinding wheel and returns to “home” or its commanded position.
7. Processes 1 and 2 signal main process that they have completed their tasks.
8. Main process completes its program execution.
9. Repeat steps 1 - 8 , as required.
The dual workhead chucker grinding machine as described above for external grinding, may be adapted, by modifications made at the manufacturing level to provide for simultaneous internal grinding of bores in a pair of workpieces.
In order to obtain this result the grinding wheel, spindle case and driving motor would be removed from the wheelhead assembly and replaced with a pair of grinding wheels, a double-shaft motor and driving belts carried on supporting structure.
As shown schematically in FIG. 6, fixed block 22 and slide 34 of the wheelhead are retained. A dual internal grinding assembly 100 is secured to the moving slide. Assembly 100 includes a double-shaft motor 102 aligned as shown in FIG. 7, with the shafts 104 , 106 driving a pair of internal grinding wheels 108 , 110 supported on arbors 112 , 114 and. extending in position for workpieces supported by the workheads to be brought into grinding contact. The wheels are driven by belts connected to pulleys 116 , 118 on shafts 104 , 106 .
In operation, movement of the dual workheads is controlled by separate and independent controls using the CNC control system as for external grinding, as described above.
Although the invention is illustrated by a specific described embodiment including numerous details, it is not to be understood as so limited, but is limited only as indicated by the appended claims.
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A grinding machine has an abrasive wheel mounted on a spindle carried by a wheelhead which provides for movement in a direction perpendicular to the spindle. A pair of workheads are separately mounted on workslides and cross slides so that the workheads may be moved along an X-axis or a Y-axis as required to bring chucks of the workheads into grinding position. Sliding movement of the workslides and cross slides is produced by ball screws powered by servo motors and mounted on bearing housings, with the ball screws propelling ball nuts connected to the slides. The machine uses CNC computerized controls, with each of the workheads having a separate and independent control. This enables attainment of a high degree of precision.
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FIELD OF APPLICATION
[0001] The present invention relates to an ink composition practically void of toxicity, particularly suitable, even if not exclusively, for surface coloring and printing on supports, wrappings and objects which are to come into contact with foods.
[0002] The materials suitable for direct contact with foods (e.g. paper or plastic material wrappings, plastic or cardboard supports or trays, etc.) are currently colored or printed by means of inks which always have a certain degree of toxicity, more or less high. For this reason, these wrappings or supports are mandatorily coated with paraffinized papers or transparent plastic films, which perform a barrier function to prevent the migration of ink components towards the foods, although allowing to appreciate, in transparency, the underlying colorings or inscriptions.
[0003] It is clear that the presence of this additional barrier layer implies additional manufacturing costs and it can make the disposal of the used containers or wrappings complicated, due to the different chemical nature of the barrier layer with respect to that of the support whereon it is applied.
[0004] Moreover, in case the barrier layer, for any reason, is damaged even only in a small portion thereof, the ink can come into contact with the food and this can cause also serious consequences for the consumer's health.
[0005] Such an occurrence is certainly unlikely during the manufacturing step of the support or wrapping, especially if good manufacturing practices are scrupulously complied with, but it becomes likely during the using step by the final consumer. For example, the tear of the barrier layer on a picnic cardboard plate, also plastic plate, when using a knife to cut a food contained in the plate is to be considered.
[0006] It is proper to finally remind that sometimes certain colored or printed supports which are not per se to come into contact with foods (and thus not coated with a barrier layer) can however come into contact with the foods. It is the case, for example, of the paper place-mats used in self-service and fast food restaurants, whereon the consumer can involuntarily let particles of food fall. Since most consumers are not aware of the fact that the above place-mats are not “for foods”—also because of the reduced size of the appropriate warning “not for foods”—the food fallen on the place-mat is often picked up again and consumed.
[0007] Other fields wherein inks are often employed which may damage, in a more or less considerable extent, the consumer's or user's health are those of cosmetic products, of toys, of colors for painting or drawing (e.g. felt-tips) and of all those products that can come into contact with mouth, mucosae and skin.
[0008] The problem underlying the present invention has thus been that of providing an ink composition with safety characteristics from the toxicological point of view such as to be used for surface coloring and printing of objects, wrappings and supports intended for coming into contact with foods or with the consumers' skin or mucosae, without any risk of toxicity for these latter.
SUMMARY OF THE INVENTION
[0009] Such a problem is solved, according to the invention, by an ink composition comprising at least one color suitable for food use and a liquid vehicle including water and an organic solvent miscible with water in a volumetric ratio variable from 15:1 to 1:10, wherein said organic solvent is ethanol or a mixture ethanol:acetone in a volumetric ratio variable from 1:2 to 3:1.
[0010] Preferably, water and the organic solvent are in a ratio variable from 12:1 to 1:7 and said organic solvent is ethanol.
[0011] The color (or dye) contained in the ink composition according to the present invention is chosen among those allowed for food use, in particular among those for which the absolute harmlessness is universally known, such as for example, among the organic ones, curcumin, riboflavin, chlorophyll and chlorophyllins and complexes thereof with copper, carotene, lycopene, xanthophylls, lutein and betanine, and, among the inorganic ones, iron oxides and hydroxides, titanium dioxide, calcium carbonate, silver, aluminum, gold.
[0012] A non limiting list of the colors allowed for food use can be derived from the Italian Ministerial Decree of 21-12-1967 and from Italian Ministerial Decree of 27-12-1996, No. 684.
[0013] The color is contained in an amount preferably comprised between 0,1 and 30%, conveniently 1-25%, by weight on the total weight of the composition. When an organic color is used, the composition preferably contains 1 to 6% of it by weight of the total weight and the liquid vehicle preferably contains water and ethanol in a volume ratio varying from 3:1 to 1:7.
[0014] When, instead, an inorganic color is used, the composition preferably contains 7 to 25% of it by weight of the total weight and the liquid vehicle preferably contains water and ethanol in a volume ratio of 12:1 to 2:1.
[0015] Conveniently, the ink composition according to the invention also contains a non-toxic thickening agent, chosen from the group comprising cellulose ethers, in particular methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and carboxymethylcellulose, cellulose esters, in particular cellulose acetate, arabic gum, shellac, polyvinylpyrrolidone, xanthane and alginates.
[0016] Preferred thickening agents are the cellulose ethers, polyvinylpyrrolidone and shellac. Methylcellulose is particularly preferred.
[0017] Preferably, the amount of the thickening agent contained in the ink composition according to the present invention is comprised between 0.1% and 20% by weight of the total weight of the composition.
[0018] A further possible component of the ink composition according to the invention is represented by tannins, preferably natural, in particular tannic acid, as fixers or however agents increasing the color fastness. When present, the tannins are contained in an amount variable from 0.1% to 10% of the total weight of the composition.
[0019] It can be useful, under certain circumstances and with particular reference to requirements of ink-jet printing, that the composition according to the invention contains agents regulating the conductivity, such as for example ammonium or alkali salts of organic acids, such as acetic, lactic and propionic acid.
[0020] The amounts of these salts in this case are generally comprised between 0.1% and 0.5% by weight on the total weight of the composition.
[0021] Finally, the ink composition according to the invention can contain an antifoam agent, for preventing the foaming of the ink during the printing step. As antifoam agent silicone compounds can be used, such as for example the DC-150 of Dow Corning, or acetylenic compounds, such as for example the antifoam agents of the SURFYNOL™ series of the firm Air Product and Chemical Co. (U.S.A.) or, advantageously, natural fatty substances such as vegetal oils or animal fats.
[0022] When they are used, these antifoam agents preferably constitute 0.01%-2.0% of the total weight of the ink composition according to the invention.
[0023] The composition according to the invention, especially in the case in which natural fatty substances are used as antifoam agents, can also contain one or more emulsifiers, selected in particular among those suitable for use with foods, such as, for example, lecithins, mono- and diglycerides of food fatty acids and esters thereof with lactic, citric and tartaric acids, sucroesters (E 473) and sucroglycerides (E 474).
[0024] For the purpose of adjusting the pH of the ink composition of the present invention and to optimize the action of certain thickening agents it may result to be convenient adding ammonia, which also has the function of regulating conductivity, and/or borax, which also acts as a preservative, and/or calcium hydroxide.
[0025] Further preservatives that may be added to the ink composition according to the invention—although the latter is generally perfectly preserved even in the absence of specific preserving agents—are the parabens, in particular methyl- and propylparaben.
[0026] The addition of polyols such as glycerol, polyglycols and propyleneglycols, acting as drying time regulating agents, may be convenient.
[0027] Finally, according to particular application needs, further components, such as perfumes, substances conferring sweet taste (e.g. glycerol), essential oils etc. can be considered in the composition according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The present invention will be further described by making reference to some examples regarding ink compositions for printing on paper or cardboard but it is to be underlined that the field of application of the ink composition according to the invention is not limited to this application but it extends also to the field of the cosmetics industry, of the colors for painting and drawing, including wall paintings, and others.
EXAMPLE 1
[0029] [0029] Erythrosin 0.35 g Methylcellulose 12.0 g Ethanol 350 ml Water 50 ml
[0030] The solution obtained by mixing the above listed components has allowed to print inscriptions and drawings practically on all the types of paper and cardboard, comprised those less porous and even those which are coated or glazed.
EXAMPLE 2
[0031] [0031] Erythrosin 0.35 g Methylcellulose 2.7 g Ethanol 43.75 ml Water 31.25 ml
[0032] This solution has resulted to be suitable for printing on papers and cardboards of medium-low porosity, comprised papers and cardboards which are shiny on one side.
EXAMPLE 3
[0033] [0033] Erythrosin 0.30 g Methylcellulose 3.9 g Ethanol 43.75 ml Water 56.25 ml
[0034] This solution is suitable for printing on papers and cardboards of medium porosity.
EXAMPLE 4
[0035] [0035] Erythrosin 0.30 g Methylcellulose 3.15 g Water 53.12 ml Ethanol 21.88 ml
[0036] This solution is suitable for printing on papers and cardboards of high porosity.
EXAMPLE 5
[0037] [0037] Erythrosin 0.35 g Methylcellulose 8.0 g Tannic Acid 2.0 g Ethanol 300 ml Water 50 ml
[0038] This solution is particularly suitable for printing on papers and cardboards of low porosity.
EXAMPLE 6
[0039] [0039] Erythrosin 0.35 g Ethanol 44 ml Water 31 ml
[0040] This solution has resulted to be suitable for printing on papers and cardboards of medium-low porosity, comprised papers and cardboards which are shiny on one side.
EXAMPLE 7
[0041] [0041] Erythrosin 0.35 g Methylcellulose 8.0 g Ethanol 200 ml Acetone 100 ml Water 50 ml
[0042] This solution is particularly suitable for printing on papers and cardboards of low porosity.
EXAMPLE 8
[0043] [0043] Red iron oxide 19.2 g Waxy shellac 17.5 g Water 53.1 ml Ethanol 5.0 ml Borax 3.2 g Lard 0.8 g Soya lecithin 0.6 g Multi-seed oil 0.4 g
[0044] This composition is suitable for printing on all kinds of paper and cellulose derivatives.
[0045] The ink composition according to the invention is suitable for coloring and printing objects, supports and wrappings of paper or plastic material, of fabrics or non-woven fabrics, in particular for use in relation with foods, both when they have to directly bear or contain foods (trays, tubs, plates, etc.) and when they can accidentally come into contact with foods (e.g. table-cloths and serviettes).
[0046] This because the ink components according to the invention are all non-toxic or even edible. Also if a certain amount of acetone had to be used for color stabilization reasons, the non-toxicity of the ink composition according to the invention would be guaranteed since the acetone is however a natural metabolite in the human body.
[0047] Another possible field of application of the ink composition according to the present invention, not strictly linked to the use in relation with foods but always within a context wherein adequate hygiene conditions are required, is represented by the printing on kitchen rolls paper, toilet paper an the like, such as on disposable coats and on disposable bed sheets of paper or of non-woven fabric.
[0048] The ink composition according to the invention is suitable for coloring or printing on materials of different porosity, being always possible to select a ratio between the aqueous solvent and the organic one such that it suits the particular porosity of the substrate to be colored or printed. To the same purpose it is also possible to carry out a proper selection of the thickening agent and/or of the stabilizing agent for the color and of the respective amounts contained in the composition.
[0049] As it has been pointed at above, the ink composition according to the invention is also suitable to be used in the field of cosmetics and of the colors for painting and drawing, including wall paintings.
[0050] As regards cosmetics, the ink composition according to the present invention, thanks to its absolute non-toxicity, is effective to be used in the production of make-up, colored lip-sticks or to carry out temporary tattoos, colorings for nails, etc.
[0051] In the field of the colors for painting or drawing the ink composition can be used inside felt-tips, in particular those to be used by children. In this case, a composition free of or poor in thickening agent will be used.
[0052] The ink composition according to the invention is also particularly effective for the production of watercolors and tempera. The possible presence of a suitable amount of methylcellulose or of another thickening agent inside the ink composition according to the invention contributes to give body and thickness to the brush stroke.
[0053] It is worth reminding also of the possibility of using the ink composition according to the present invention for the coloring of wood or cardboard toys, obviously subject to being brought into contact with the mouth of children.
[0054] Always as regards wood items, the ink composition according to the invention can be used for coloring chopping boards and similar wood tools used in the kitchen, such as wood trays, also thanks to the good capacity of impregnation that it has demonstrated towards the wood.
[0055] Finally, the composition according to the present invention, thanks to its absolute harmlessness and “naturalness”, could be used for coloring any item, object or packaging, even if not expressly intended for being used in relation with foods, by those firms which desire to convey a message of maximum respect for the environment and for health to the potential buyers.
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An ink composition comprising at least one color suitable for food use and a liquid vehicle including water and an organic solvent miscible with water in a volumetric ratio variable from 3:1 to 1:10, wherein the organic solvent is ethanol or a mixture ethanol:acetone in a volumetric ratio variable from 1:2 to 3:1; this ink composition is suitable, in particular, even though not exclusively, for surface coloring and printing on supports, wrappings and objects intended for coming into contact with foods.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to LCD monitors and more particularly, to a LCD monitor that has multiple background colors.
[0003] 2. Description of the Related Art
[0004] A regular LCD monitor has a reflector at the back side to reflect light from the backlight module, thereby enhancing the background light. However, the whole display panel of a conventional LCD monitor simply provided one background color, light grey or yellow. This monochromic background color is monotonous, showing little visual effect.
SUMMARY OF THE INVENTION
[0005] The present invention has been accomplished under the circumstances in view. It is therefore the main object of the present invention to provide a LCD monitor, which shows different background colors in multiple display zones on the LCD panel. According to the present invention, the LCD monitor comprises a plurality of light guides arranged on a bottom side of a LCD panel thereof, multiple LED (light emitting diode) lamps respectively arranged at one side of each of the light guides and controllable to emit different colors of light to the light guides respectively for showing different background colors in different display zones on the LCD panel, and multiple blocking filters respectively attached to the periphery of the light guides to block the light of the LED lamps in the associating light guides respectively and to prohibit the light of each of the LED lamps from passing out of the associating light guide.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is an exploded view of the preferred embodiment of the present invention.
[0007] FIG. 2 is a front view of the preferred embodiment of the present invention.
[0008] FIG. 3 is a sectional assembly view of the preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0009] Referring to FIGS. 1˜3 , a LCD monitor in accordance with the present invention is shown comprising a LCD panel 10 , a plurality of light guides 21 ˜ 26 arranged on the bottom side of the LCD panel 10 , multiple LED (light emitting diode) lamps 27 respectively arranged at one side of each of the light guides 21 ˜ 26 and controlled to emit different colors of light to the associating light guides 21 ˜ 26 , and multiple blocking filters 20 respectively attached to the periphery of the light guides 21 ˜ 26 to block the light of the associating LED lamp 27 in the associating light guide and to prohibit the light of the associating LED lamp 27 from passing through the other light guides.
[0010] Referring to FIGS. 2 and 3 again, the light guides 21 ˜ 26 , the blocking filters 20 and the LED lamp 27 are abutted against one another on a same plane, and then covered with a light diffuser film 18 at the top side and a light reflector film 28 at the bottom side, and then the LCD panel 10 is attached to the top side of the light diffuser film 18 , and then the assembly thus obtained is installed in a circuit board 30 and packed in a frame 31 . Thus, the LCD panel 10 and the LED lamps 27 are electrically connected to the circuit board 30 , and the circuit board 30 provides the necessary working voltage to the LCD panel 10 and the LED lamps 27 .
[0011] Further, the LCD panel 10 has multiple display zones 11 ˜ 16 corresponding to the light guides 21 ˜ 26 . The display zones 11 ˜ 16 each has bright dots 17 controllable by the circuit board 30 to display or not to display letters or graphics (because the function of the bright dots of the LCD panel 10 to display or not to display is of the known art and not within the scope of the present invention, no further detailed description in this regard is necessary). For example, the first display zone 11 is adapted to display English letters; the second display zone 12 is adapted to display graphics; the third through sixth display zones 13 ˜ 16 are adapted to display numerals.
[0012] When the LED lamps 27 are turned on, the light of the LED lamps 27 passes through the associating light guides 21 ˜ 26 , the light reflector film 28 reflects light toward the light diffuser film 18 , and the light diffuser film 18 diffuses light into the whole area of the LCD panel 10 . Further, the LED lamps 27 can be controlled to emit different colors of light into the associating light guides 21 ˜ 26 . By means of the effect of the blocking filters 20 , each of the light guides 21 ˜ 26 is illuminated with a respective color of light, and therefore the display zones 11 ˜ 16 of the LCD panel 10 show different background colors A˜F, showing a unique visual effect.
[0013] Although a particular embodiment of the invention has been described in detail for purposes of illustration, various modifications and enhancements may be made without departing from the spirit and scope of the invention.
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A LCD monitor, which has multiple light guides matched with a respective LED lamp and peripherally blocked with light blocking filters so that different background colors are shown in different display zones of the LCD panel thereof.
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[0001] This is a complete application claiming benefit of provisional application Ser. No. 60/371,154 filed Apr. 10, 2002.
BACKGROUND OF THE INVENTION
[0002] 1. Technical Field
[0003] The instant invention relates to unique polymeric bicomponent fibers and to the production of wicking devices, especially, nibs and ink reservoirs for writing and marking instruments made from such fibers. More specifically, this invention is directed to the production and use of nibs and ink reservoirs, particularly nibs for writing and marking instruments such as fiber tip pens and “felt tip” markers, as well as roller ball wicks for roller ball pens, wherein the wicking devices are formed of sheath-core, melt blown, bicomponent fibers wherein a core of a nylon 6,6 is substantially fully covered with a sheath of polyethylene terephthalate or a copolymer thereof. For the production of nibs, the core material may be polybutylene terephthalate.
[0004] 2. Discussion of the Prior Art
[0005] The production of thermally bonded fibrous products for various applications is disclosed in commonly assigned U.S. Pat. No. 5,607,766 issued Mar. 4, 1997 (the subject matter of which is incorporated herein in its entirety by reference) (the '766 patent) using bicomponent fibers comprising a coating of a polyester sheath, such as polyethylene terephthalate and its copolymers, over a thermoplastic core, such as polypropylene and polybutylene terephthalate. There are currently commercial permanent ink markers using nibs made of polyester felt impregnated with phenolic resin which have an aggressive xylene-based ink formulation. Past attempts to produce nibs formed of bonded polyester fiber tows, particularly for use with writing and marking instruments incorporating such aggressive inks, have suffered unacceptable “drainback” properties. A drainback test is where the marker is stood on end, tip up, for 48 hours. It is then inverted (tip down). The pen must write on the third stroke to pass the test. While currently available polyester felt/phenolic nibs satisfy commercial drainback criteria, early polyester filament-based attempts to reproduce these properties failed.
[0006] Although core materials of polybutylene terephthalate, as disclosed in the '766 patent, show desirable properties for use as reservoirs in writing and marking instruments and the polyester/polypropylene bicomponent fiber products discussed therein are acceptable for selected applications, both polypropylene and nylon 6 core materials in polyester sheath bicomponent fiber thermally bonded writing and marking instrument components have now been found to unduly soften in the presence of certain particularly aggressive ink formulations, making marking and writing instrument components, particularly nibs, formed of bicomponent fibers having polyester sheaths with such core polymers of limited utility and, from a commercial standpoint, effectively useless.
[0007] This invention relates to the surprising discovery that, in the production of nibs for writing instruments, such as roller ball or fiber-point pens, or marking instruments, such as felt-tipped permanent highlighters, dry-erase markers and the like, especially those incorporating aggressive inks such as xylene-based permanent ink formulations, the use of a bonded fibrous element formed from melt blown bicomponent fibers comprising a polyester sheath and a nylon 6,6 or polybutylene terephthalate core material provides excellent drainback and ink laydown properties, thermal stability and physical robustness. Use of bonded fiber tow materials, even bicomponent fiber tows having a polyester sheath over a nylon 6,6 core, will fail the drainback test, but melt blown bicomponent fibers of these polymers produce acceptable nibs for writing and marking instruments.
[0008] Such products also have unexpectedly improved solvent resistence and increased stiffness avoiding degradation under pressure in use. Moreover, these unique bicomponent fibers produces writing and marking instrument components which are less expensive than competitive products, such as the polyester felt/phenolic nibs currently in the market. Similar advantages are expected for ink reservoirs formed of melt blown polyester/nylon 6,6 bicomponent fibers.
OBJECTS AND SUMMARY OF THE INVENTION
[0009] It is, therefore, a principal object of the instant invention to provide a method and apparatus for making writing and marking instrument components in a simple, efficient and inexpensive manner, yet having the property of unexpectedly improved drainback, exceptional solvent resistance in the presence of highly aggressive ink formulations, and increased stiffness and robustness, resisting degradation under pressure, particularly when used as a nib.
[0010] Another object of this invention is the provision of melt blown polymeric bicomponent fibers having a polyester sheath, particularly polyethylene terephthalate and copolymers thereof, totally surrounding a core of nylon 6,6, and the production of thermally bonded porous fibrous products for use as a nib, roller ball wick or ink reservoir in a writing or marking instrument which will not be significantly softened by the solvent in the ink and function effectively to retain and controllably feed ink from a reservoir to a writing surface even after extended use.
[0011] Yet another object of this invention is the provision of a writing instrument and/or a marker incorporating a nib, roller ball wick and/or an ink reservoir formed as a thermally stable, three-dimensional, porous element capable of storing and/or controllably releasing and feeding a liquid ink formulation with little or no drainback.
[0012] A further object of this invention is the provision of a high capacity ink reservoir for a writing or marking instrument defined by an elongated porous rod formed of a network of fine melt blown bicomponent fibers having a continuous sheath of polyethylene terephthalate or a copolymer thereof, and a core of nylon 6,6, and a nib for a roller ball or fiber-point pen or a felt-tipped marker, or the like, which are compatible with all currently-available ink formulations and provide an adequate release pressure to minimize “leakers” and “drainback”, and remain functionally effective over extended periods of use.
[0013] Upon further study of the specification and the appended claims, additional objects and advantages of this invention will become apparent to those skilled in the art.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] These and other objects, features and many of the attendant advantages of this invention will be better understood by those with ordinary skill in the art in connection with the following detailed description of the preferred embodiments and the accompanying drawings wherein:
[0015] FIG. 1 is an enlarged perspective view of one form of a “sheath-core” bicomponent fiber according to the instant invention;
[0016] FIG. 2 is a perspective view of an ink reservoir element made therefrom;
[0017] FIG. 3 is a side elevational view of an ink reservoir element including a longitudinally continuous peripheral air passageway integrally formed therein;
[0018] FIG. 4 is an enlarged transverse cross-sectional view taken along lines 4 - 4 of FIG. 3 ;
[0019] FIG. 5 is a cross-sectional view, partially broken away, of one form of a writing instrument in the nature of a roller ball disposable pen incorporating an ink reservoir, and a roller ball fiber wick made according to the instant inventive concepts;
[0020] FIG. 6 is a side elevational view, partially broken away, of a marking instrument in the nature of a “felt tip” marker, also incorporating an ink reservoir and a fibrous nib made according to the instant inventive concepts;
[0021] FIG. 7 is a perspective view of the nib portion of the marker of FIG. 6 ; and
[0022] FIG. 8 is a side elevational view of a nib to be used in a fiber-point pen according to this invention.
[0023] Like reference characters refer to like parts throughout the several views of the drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] The instant inventive concepts are embodied in a bicomponent, sheath-core, melt blown, fiber as seen schematically, very enlarged, at 20 in FIG. 1 wherein the core 24 is formed of nylon 6,6 and the sheath 22 is formed of polyethylene terephthalate or a copolymer thereof.
[0025] As defined in the '766 patent, the term “bicomponent” as used herein refers to the use of two polymers of different chemical nature placed in discrete portions of a fiber structure. While other forms of bicomponent fibers are possible, the more common techniques produce either “side-by-side” or “sheath-core” relationships between the two polymers. The instant invention is concerned with the production of “sheath-core” bicomponent fibers wherein a sheath of polyethylene terephthalate or a copolymer thereof is spun to completely cover and encompass a core of nylon 6,6 or polybutylene terephthalate, preferably using a “melt blown” fiber process to attenuate the extruded fiber.
[0026] As defined in the '766 patent, the term “polyethylene terephthalate or a copolymer thereof” refers to a homopolymer of polyethylene terephthalate or a copolymer thereof having a melting point which is higher than the melting point of the thermoplastic core material in the bicomponent fiber.
[0027] Conventional linear polyester used to make fibers is the product of reaction of ethylene glycol (1,2 ethanediol) and terephthalic acid (benezene-para-dicarboxylic acid). Each of these molecules has reactive sites at opposite ends. In this way, the larger molecule resulting from an initial reaction can react again in the same manner, resulting in long chains made of repeated units or “mets”. The same polymer is also industrially made with ethylene glycol and dimethyl terephthalate (dimethyl benezene-paradicarboxylate). It is believed that polyethylene terephthalate and its copolymer of a broad range of intrinsic viscosities are useful according to this invention, although those with lower intrinsic viscosities are preferred.
[0028] By partially substituting another diol for the ethylene glycol or another diacid for the terephthalic acid, a more irregular “copolymer” is obtained. The same effect is achieved by the substitution of another dimethyl ester for the dimethyl terephthalate. Thus, there is a wide choice of alternative reactants and of levels of substitution.
[0029] The deviation from a regularly repeating, linear polymer makes the crystallization more difficult (less rapid) and less complete. This is reflected in a lower and wider melting range. Excessive substitution will result in a totally amorphous polymer which is unacceptable for use in this invention.
[0030] As defined in the '766 patent, the term “melt blown” refers to the use of a high pressure gas stream at the exit of a fiber extrusion die to attenuate or thin out the fibers while they are in their molten state. Melt blowing of single polymer component fibers was initiated at the Naval Research Laboratory in 1951. The results of this investigation were published in Industrial Engineering Chemistry 48, 1342 (1956). Seven years later, Exxon completed the first large semiworks melt blown unit demonstration. See, for example, Buntin U.S. Pat. Nos. 3,595,245, 3,615,995 and 3,972,759 (the '245, '995 and '759 patents, the subject matters of which are incorporated herein in their entirety by reference) for a comprehensive discussion of the melt-blowing process. Although the average diameter of the bicomponent fibers can vary over a significant range without departing from the instant inventive concepts, fine fibers, on the order of about 10 microns, as produced by conventional melt blowing techniques are particularly useful. Specific apparatus and techniques for producing such fibers are found in the '766 patent.
[0031] The term “nylon 6,6” as used herein refers to a polymer of adipic acid and hexamethylene diamine. The nylon 6,6 used was DuPont Zytel 101, unfilled, with a melt viscosity range of 88-124 pascal-seconds.
[0032] An ink reservoir 25 as seen in FIG. 2 comprises an elongated air-permeable body of fine melt blown bicomponent polyethylene terephthalate/nylon 6,6 fibers such as shown at 20 in FIG. 1 , bonded at their contact points to define a high surface area, highly porous, self-sustaining element having excellent capillary properties using the techniques disclosed in the '766 patent. It is to be understood that elements 25 produced in accordance with this invention need not be of uniform construction throughout as illustrated in FIG. 2 . For example, a continuous longitudinally extending peripheral groove such as seen at 26 in FIGS. 3 and 4 can be provided as an air passage in an ink reservoir 30 , which may or may not include a coating or film wrap (not shown).
[0033] The reservoir 30 may be incorporated into a writing instrument as shown in FIG. 5 which is illustrated as including a roller ball wick 36 , which can also be produced by the techniques of this invention, extending into a roller ball writing tip 38 in a conventional manner. The ink reservoir 35 is contained within a barrel 40 in fluid communication with the roller ball wick 36 to controllably release a quantity of ink retained in the reservoir 30 to the roller ball 42 in the usual way.
[0034] As is well known in the art, the roller ball wick 36 will generally have a higher capillarity than the reservoir 30 , with the fibers thereof being more longitudinally oriented so as to draw the ink form the reservoir 30 and feed the same to the roller ball 42 . It is well within the skill of the art to form the three-dimensional porous elements of the instant invention with higher or lower capillarity depending upon the particular application by controlling, for example, the speed with which the fibrous mass is fed into the forming devices, the size and shape of the forming devices and other such obvious processing parameters.
[0035] In FIG. 6 , a marking device is shown generally at 50 , as including a conventional barrel 52 , containing an ink reservoir 55 in fluid communication with a fibrous wick or nib 54 seen in perspective in FIG. 7 , which may be of the type commonly referred to as a “felt tip”. Again, the nib 54 is generally denser, than the fibers from which the reservoir 55 are made, in order to provide the nib with the higher capillarity necessary to draw the ink from the reservoir in use.
[0036] A fiber tip 60 seen in FIG. 8 can also be provided according to his invention for use in lieu of the roller ball wick 36 of FIG. 5 or the felt tip nib 54 of FIG. 6 in the production of a fiber-point pen in a well known manner.
[0037] The angled felt-tip nib 54 and the pointed fiber tip 60 can be provided with the shapes shown, or any other desired shape, by conventional cutting, grinding or other techniques well known to those skilled in the art.
[0038] While reference has been made herein to the provision of writing and marking instrument nibs and reservoirs made of melt blown, bicomponent sheath/core polyethylene terephthalate/nylon 6,6 fibers according to this invention, it is to be understood that the nibs of this invention can be used effectively with other reservoirs, even in the presence of aggressive ink formulations, since the reservoirs are not subjected to the pressure experienced by the nibs in use and need not be as robust. Moreover, although polyethylene terephthalate/polybutylene terephthalate ink reservoirs are suggested in the '766 patent, it is surprising that such bicomponent fibers can satisfy the more rigorous requirements of a nib for a writing or marking instrument since the use of the other core polymers referenced in the '766 patent are not acceptable for this purpose as explained below. It will also be understood that reservoirs formed of polyester/nylon 6.6 fibers according to this invention are expected to have advantages, even for use with nibs made of prior art materials.
[0039] To compare the properties of nibs made by this invention with nibs made of melt blown bicomponent polyester sheath fibers with different core materials, square stock, angularly cut nibs typical of marker “felt tip” pens, were made from melt blown polyethylene terephthalate (PET)/polypropylene (PP) (25/75) sheath-core bicomponent fibers using the general techniques disclosed in the '766 patent, cut with a razor blade at a 45° angle, and inserted into Sanford King Size item number 15000 permanent markers after the commercial nibs were removed. This enabled testing in the exact ink and marker environment. Comparable products were made from melt blown bicomponent fibers comprising PET sheath materials covering, respectively, polybutylene terephthalate (Ticona PBT), nylon (BASF Ultramin) and nylon 6,6 Dupont Zytel).
[0040] All samples spun well, with the PET/PBT and PET/Nylon 6,6 bonding acceptably. PET/Nylon 6 bonding behavior was poorer than the other samples. The PET/nylon 6 nibs were attacked by the ink in a manner similar to PET/PP. Because of this, these pieces were not tested further.
[0041] Samples were run at a variety of densities. These densities (all in g/10 pieces) were:
PET/PBT: 5, 6, 7 PET/Nylon 6,6 (melt blown): 4.5, 5, 6.5
[0042] For the most part, with the exceptions noted below, the density can be varied over a significant range depending upon the particular application of the final product.
[0043] Summary results are:
Criteria Store bought PET/PBT PET/Nylon 6,6 (melt blown) 48 softening Pass Pass Pass 48 hour drainback Pass Pass (high density (7) failed) Pass Hand write (will the nib pass ink to paper) Pass Pass Pass Firmness after 48 hours (subjective) Pass Pass (some had slightly soft tips) Pass (some had slightly soft tips) Bleed through Pass Pass Pass Write after 60° C., 5 days Pass Pass (except at 7 density) Pass Firmness after 60°, 5 days Pass Slightly feathered Pass Firmness after 100 meter writing test Worn down No impact to feathered Slightly to heavily feathered Cap off (dryout) test (1 hour in hood) All fail Some pass, some fail Some pass, some fail
[0044] The above tests show that, unlike the PET/PP and PET/nylon 6 samples which were unacceptably softened by the ink and commercially useless as nibs for marking instruments, the PET/nylon 6,6 nibs (as well as the PET/PBT nibs), for the most part, compared favorably with commercial polyester felt/phenolic nibs in each of the tested properties. From a manufacturing standpoint, use of the melt blown process according to this invention enables the creation of finished marker nibs from polymer chip in a continuous manner eliminating the prior art techniques of fiber spinning, felting, forming, resin impregnation and cutting. As a result, significant economies should be achieved, with savings of from 20-50% possible.
[0045] Nibs made from the same polymeric components, i.e., PET over nylon 6,6, but of a bonded fiber tow rather than melt blown fibers, fail to provide commercially acceptable drainback properties. Although the rationale for this surprising result is not known for certain, it is theorized that the improved tortuous path characteristics of the melt blown web enhance the drainback properties of the resultant nibs.
[0046] The foregoing descriptions and drawings should be considered as illustrative only of the principles of the invention. Numerous applications of the present invention will readily occur to those skilled in the art. Therefore, it is not desired to limit the invention to the preferred embodiments or the exact construction and operation of the preferred apparatus shown and described. Rather, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention.
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A high strength wick is presented that comprises a self-sustaining fibrous element. This element is formed of a multiplicity of fibers bonded to each other at spaced apart points of contact to define a porous matrix. The fibers are melt blown bicomponent fibers comprising a core of nylon 6,6 and a sheath of a polymer selected from the group consisting of polyethylene terephthalate and copolymers of polyethylene terephthalate. The sheath polymer is selected and adapted for solvent resistance.
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BACKGROUND OF THE INVENTION
The present invention relates generally to the art of surgical gowns and the like folded for aseptic donning. More particularly, the invention relates to an improved folded surgical gown, as well as improved apparatus and methodology for producing same.
Generally, surgeons and other medical professionals will wear an overgarment during operating procedures both to enhance the sterile condition in the operating room and to protect the underclothes of the wearer. The overgarment is typically configured as a gown having a main body portion to which respective sleeves are attached. According to modern practice, the gowns are often made from a breathable nonwoven barrier material and are intended to be disposable.
Surgical gowns of this type are often packaged and presented to the wearer in a "book-fold" arrangement. In such an arrangement, exterior surfaces of the gown are contained largely inside the folded garment. Hand pockets are located on each side of the folded garment for receipt of the wearer's respective hands. As the hands are lifted up and out, the gown will unfold and fall into place on the wearer's body.
A known process for producing a folded surgical gown having a book-fold arrangement is disclosed in U.S. Pat. No. 3,359,569 to Rotanz et al. According to this technique, the gown is folded upward a plurality of times and the sleeves are folded in half. Final folds are made by folding the gown inward a number of times until the gown resembles the shape of a book. Hand pockets are formed on opposite sides of the gown to enable aseptic donning in the manner described above.
While the technique shown in Rotanz is effective at producing a folded surgical gown for aseptic donning, it is not without disadvantages. Notably, the fold sequence is difficult to replicate on automated equipment. As a result, manual labor, with its inherent costs and other inefficiencies, has generally been used to produce the folded garment.
SUMMARY OF THE INVENTION
The present invention recognizes and addresses the foregoing disadvantages, and others, of prior art constructions and methods. Accordingly, it is an object of the present invention to produce a surgical gown in an improved folded arrangement.
It is a further object of the present invention to produce a surgical gown in an improved folded arrangement which also has opposed hand pockets for aseptic donning.
It is a further object of the present invention to produce a surgical gown in an improved folded arrangement that can be efficiently produced utilizing automated equipment.
It is also an object of the present invention to provide improved methodology for producing a folded surgical gown.
It is also an object of the present invention to provide apparatus for producing a folded surgical gown.
Some of these objects are achieved by a surgical gown comprising a main gown configured to cover a predetermined area of a wearer's body. The main gown includes a back portion, and an opposed front portion having respective left and right flaps. Left and right sleeves are attached to the main gown to extend from respective lateral sides thereof.
The surgical gown is folded in a manner in which each flap is turned at least partially back upon itself to expose an interior surface of the main gown. The sleeves are each folded behind the back portion of the main gown. The main gown is also back folded along first and second longitudinal fold lines extending substantially parallel to the lateral sides thereof. In addition, the main gown is back folded after folding along the longitudinal fold lines along at least one transverse fold line substantially transverse to the lateral sides of the main gown to define left and right hand pockets. The main gown is further folded along a third longitudinal fold line to form a folded surgical gown such that respective hand pockets are located on opposite sides thereof.
In exemplary embodiments, the main gown is back folded along first and second transverse fold lines after being back folded along the first and second longitudinal fold lines. Preferably, the main gown is further back folded along an initial transverse fold line before being back folded along the first and second longitudinal fold lines. For example, the section of the main gown folded along the initial transverse fold line may have a longitudinal length of between one-fourth and one-half the initial longitudinal length. The resulting longitudinal length may then be folded into thirds along the first and second transverse fold lines, thereby yielding a longitudinal length less than one-fourth the original longitudinal length of the main gown. In addition, the sleeves may be folded behind the back portion of the main gown before the main gown is folded along the initial transverse fold line.
The sleeves of the surgical gown are preferably folded behind the back portion of the main gown at an acute angle from a transverse dimension of the main gown. For example, the sleeves may each be folded in at the lateral sides of the main gown to completely cross one another behind the back portion of the main gown. Alternatively, the sleeves may each be folded in at the lateral sides of the main gown and out at an intermediate location thereof back toward the lateral sides.
Other objects of the invention are achieved by an apparatus for folding a garment having a main gown to which left and right sleeves are attached and comprising a plurality of operative sections arranged in series. In particular, the apparatus includes an infeed section having a platen surface adapted to horizontally support the main gown of the garment such that the sleeves hang vertically therefrom. A sleeve-tucking section is provided, operative to fold the sleeves behind a back portion of the main gown. A longitudinal folding section is operative to fold the main gown along first and second longitudinal fold lines to thereby decrease a transverse width of the garment. A transverse folding section, preferably operatively succeeding the longitudinal folding section, folds the main gown along at least one transverse fold line to form a folded garment.
In exemplary embodiments, the apparatus includes a support element, located at an output of the transverse folding section, to which the garment is delivered. The support element preferably includes a longitudinal folding bar about which a manual longitudinal fold may be made.
The transverse folding section is preferably operative to fold the main gown along at least two transverse fold lines. Toward this end, preferred embodiments of the transverse folding section comprise first and second folding nips located opposite respective first and second downslope conveyors. First and second reciprocative elements are provided to operatively engage the garment along a respective transverse fold line and move it into an associated folding nip.
In some exemplary embodiments, the infeed section delivers the garment to the sleeve-tucking section in a manner that forms an initial transverse fold in the garment. For example, the platen surface of the infeed section may be reciprocatively movable to and from a location adjacent a nip defined at an entrance of the sleeve-tucking section.
The sleeve-tucking section may be constructed including a first dead plate of a width approximately equal to the garment. A first conveyor is spaced slightly above and opposing the first dead plate to move the garment therealong. Similarly, the longitudinal folding section may include a second dead plate of a width less than the garment. A second conveyor is spaced slightly above and opposing the second dead plate to also move the garment.
In such embodiments, the sleeve-tucking section may be constructed having first and second movable sleeve tuckers located below opposite lateral sides of the first dead plate. The longitudinal folding section may include first and second fixed folder plates located below the second dead plate.
Still further objects of the invention are achieved by an apparatus for folding a garment. The apparatus comprises an infeed section having a horizontal platen surface reciprocatively movable between a recess position and a garment delivery position.
A longitudinal folding section is further provided, including a lesser width dead plate having a width less than the garment. A conveyor opposes the lesser width dead plate to move the garment therealong. The longitudinal folding section further includes first and second folder plates located below the lesser width dead plate.
The apparatus includes a transverse folding section having first and second folding nips located opposite respective first and second downslope conveyors. In addition, first and second reciprocative elements operatively engage the garment along a transverse fold line and move it into a respective folding nip. A support element is provided at an output of the transverse folding section to which the garment is delivered.
In some exemplary embodiments, the apparatus may include a sleeve-tucking section operatively preceding the longitudinal folding section. The sleeve-tucking section functions to fold sleeves of the garment behind a back portion thereof.
Preferably, the sleeve-tucking section includes a greater width dead plate of a width approximately equal to the garment. A further conveyor is provided in such embodiments to oppose the greater width dead plate to move the garment therealong. The sleeve-tucking section preferably comprises first and second movable sleeve tuckers located below opposite lateral sides of the greater width dead plate. The infeed section may be configured in such embodiments to deliver the garment to the sleeve-tucking section in a manner that forms a transverse fold in the garment.
Additional objects of the invention are achieved by a method of folding a surgical gown having a main gown to which respective left and right sleeves are attached. One step of the method involves folding left and right flaps of the main gown at least partially back upon themselves to expose an interior surface of the main gown. Another step of the method involves folding the sleeves behind a back portion of the main gown.
The main gown is further folded back along first and second longitudinal fold lines extending substantially parallel to respective lateral sides thereof. After folding along the first and second longitudinal fold lines, the main gown is folded back along at least one transverse fold line extending substantially transverse to the lateral sides of the main gown to define left and right hand pockets. Finally, the main gown is folded along a third longitudinal fold line to form a folded surgical gown such that the hand pockets are located on opposite sides thereof.
According to presently preferred methodology, the main gown is folded back along first and second transverse fold lines after being folded along the first and second longitudinal fold lines. Preferably, the main gown is further folded back along an initial transverse fold line before being folded along the first and second longitudinal fold lines. For example, the main gown may be folded along the initial and first and second transverse fold lines into a length of less than approximately one-fourth the original longitudinal length.
As an additional method step, the sleeves may be folded behind the back portion of the main gown before the main gown is folded along the initial transverse fold line. In this regard, the sleeves may be folded behind the back portion of the main gown at an acute angle from a transverse dimension of the main gown. For example, the sleeves may each be folded in at the lateral sides of the main gown to completely cross one another behind the back portion of the main gown. Alternatively, the sleeves may each be folded in at the lateral sides of the main gown and out at an intermediate location thereof back toward the lateral sides.
Other objects of the invention are achieved by a method of folding a long-sleeved garment having a back portion and an opposed front portion defining left and right flaps. One step of the method involves folding the flaps at least partially back upon themselves to expose an interior surface of the garment. As an additional step, the sleeves are folded behind the back portion at an acute angle to a transverse dimension thereof.
As a further step, a selected length of the garment is folded back along an initial transverse fold. The garment is also back folded along first and second longitudinal fold lines extending substantially parallel to respective lateral sides thereof. In addition, the garment is folded back along two subsequent transverse fold lines extending substantially transverse to the lateral sides such that the garment has a longitudinal length of less than approximately one-fourth an original longitudinal length thereof.
According to presently preferred methodology, the garment is further folded along a central longitudinal fold line to form a folded garment wherein left and right hand pockets are located on opposite sides thereof. Donning of the garment is thus facilitated by a wearer without touching an outer surface of the garment.
Other objects, features and aspects of the present invention are provided by various combinations and subcombinations of the disclosed elements, as well as methods of utilizing same, which are discussed in greater detail below.
BRIEF DESCRIPTION OF THE DRAWINGS
A full and enabling disclosure of the present invention, including the best mode thereof, to one skilled in the art, is set forth more particularly in the remainder of the specification, including reference to the accompanying drawings, in which:
FIG. 1 is a perspective view of a surgical gown folded according to the present invention showing insertion of a wearer's hands into respective hand pockets thereof;
FIG. 2 illustrates aseptic donning of the surgical gown of FIG. 1 by a wearer;
FIGS. 3A through 3H illustrate folding of a surgical gown according to the present invention to achieve an improved folded arrangement;
FIG. 4 is a perspective view of an apparatus constructed in accordance with the present invention for producing a folded garment;
FIG. 5 is a perspective view of an infeed section of the apparatus of FIG. 4;
FIG. 6 is a perspective view illustrating the operative relationship between the infeed section and a sleeve-tucking section of the apparatus of FIG. 4;
FIGS. 7A and 7B are perspective views illustrating operation of the sleeve-tucking section of the apparatus of FIG. 4;
FIGS. 8A through 8C are perspective views illustrating operation of a longitudinal folding section of the apparatus of FIG. 4;
FIG. 9 is a perspective view illustrating the operative relationship between the longitudinal folding section and a transverse folding section of the apparatus of FIG. 4;
FIG. 9A is an enlarged perspective view of a preferred reciprocative mechanism utilized in the transverse folding section of FIG. 9;
FIGS. 10A through 10E are elevational views illustrating operation of the transverse folding section of the apparatus of FIG. 4;
FIG. 11 is an elevational view showing delivery of a garment from a output of the transverse folding section to a support element of the apparatus of FIG. 4; and
FIG. 12 is a perspective view illustrating use of the support element to manually form a final fold in the garment.
Repeat use of reference characters in the present specification and drawings is intended to represent same or analogous features or elements of the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
It is to be understood by one of skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention, which broader aspects are embodied in the exemplary constructions.
Referring to FIG. 1, a surgical gown 10 is shown in an improved folded arrangement produced according to the present invention. Like prior art "book-folds," exterior surfaces of the gown are contained largely within the folded garment. Left and right hand pockets 12 and 14 are also provided on opposite sides of the folded garment for receipt of respective hands 16 and 18 of the wearer.
As with prior art book-folds, the illustrated arrangement allows aseptic donning of gown 10 by a medical professional. First, the wearer's hands 16 and 18 are inserted into respective hand pockets 12 and 14. Next, as shown in FIG. 2, wearer 20 lifts gown 10 with arms separated, causing gown 10 to unfold. Gown 10 then falls into place about the shoulders of wearer 20. Significantly, wearer 20 thus dons gown 10 without touching the gown's exterior surface.
Referring now to FIG. 3A, gown 10 is shown lying substantially flat. Gown 10 includes a main gown 22 constructed in this case as a unitary sheet having a back portion 24 and an opposed front portion comprising left and right flaps 26 and 28. It will be appreciated that the terms "front portion" and "back portion" are merely a matter of convention adopted for purposes of explanation. Typically, the "back portion" will cover the wearer's chest, whereas the "front portion" will be behind the wearer.
Gown 10 further includes a pair of sleeves 30 and 32 attached to main gown 22 by appropriate means, such as stitching 34. In this case, sleeves 30 and 32 are equipped with respective cuffs 36 and 38 at the distal ends thereof. Preferably, cuffs 36 and 38 may be made from knitted fabric, whereas the remainder of gown 10 will be nonwoven. The nonwoven material chosen for this purpose is preferably of a type which is breathable from the inside, while being reasonably impervious to fluid penetration from the outside.
A reinforced collar 40, also preferably nonwoven, may be stitched or otherwise suitably attached along the upper portion of main gown 22. In addition, gown 10 will often be equipped with a pair of straps 42 and 44 initially extending behind back portion 24 as shown, where they are retained by a retaining tag 46. Straps 42 and 46 will often be attached to the insides of flaps 26 and 28 by respective tape pieces 48 and 50. Other suitable means may also be utilized, however, for attaching straps 42 and 44.
When gown 10 is donned, another medical professional (other than the wearer) will typically pull retaining tag 46, freeing the respective straps 42 and 44. Straps 42 and 44 can then be brought around the wearer's back and tied off to prevent inadvertent doffing of the gown.
A preferred manner in which gown 10 may be folded is illustrated in FIGS. 3A through 3H. Referring particularly to FIG. 3A, flaps 26 and 28 are first folded at least partially back upon themselves, as indicated at 52 and 54, to expose the interior surface of gown 10.
In this case, main gown 22 is folded back along an initial transverse fold line t i , as indicated in FIG. 3B at 56. Preferably, the longitudinal length of the section folded behind back portion 24 in this manner will be between one-fourth and one-half the overall longitudinal length of main gown 22. For example, the section so folded may extend almost back to collar 40.
Referring now to FIGS. 3C and 3D, sleeves 30 and 32 are folded behind back portion 24 at an acute angle Θ from the transverse dimension of main gown 24. In FIG. 3C, sleeves 30 and 32 are folded inward at a location adjacent the lateral sides of main gown 22 as indicated at 58 and 60, and outward at an intermediate location as indicated at 62 and 64. As shown in FIG. 3D, sleeves 30 and 32 may alternatively be folded only inward to cross one another. Sleeve folding may occur either before or after the initial transverse fold shown in FIG. 3B, depending on the exigencies of a particular application.
As shown in FIG. 3E, main gown 22 is then back folded as indicated at 62 and 64 along a pair of longitudinal fold lines l 1 and l 2 . Next, as indicated at 66 in FIG. 3F, a selected length of main gown 22 is back folded along a transverse fold line t 1 . Another selected length of main gown 22 is then folded along an additional transverse fold line t 2 , as shown at 68 of FIG. 3G.
Preferably, the length of main gown folded at both t 1 and t 2 will be approximately one-third the remaining longitudinal length of main gown 22 after the fold at t i has been effected. The resulting folded garment will thus have a longitudinal length less than approximately one-fourth the original length of main gown 22. The transverse width of the folded garment at this stage will be defined by the width remaining after the folds along l 1 and l 2 .
Apparent at this stage in the folded garment are hand pockets 12 and 14, which are formed under flaps 26 and 28. As shown in FIG. 3H, the final "book-fold" arrangement is produced by a single fold along a central longitudinal fold line l c . In other words, further folding as indicated at 70 and 72 will place hand pockets 12 and 14 on opposite sides of the garment, as desired.
In contrast to the prior art, the folding sequence shown in FIGS. 3A through 3H is particularly amenable to automated processing. In this regard, FIG. 4 illustrates a preferred embodiment of an apparatus 74 for producing such a folded garment. As can be seen, apparatus 74 includes a number of functional sections arranged in series from an input end 76 to an output end 78. These functional sections include an infeed section 80, a sleeve-tucking section 82, a longitudinal folding section 84 and a transverse folding section 86.
Turning now to FIG. 5, infeed section 80 is shown in greater detail. Infeed section 80 includes a platen surface 88 onto which gown 10 is placed at the beginning of the folding sequence. Surface 88 is preferably sized so that sleeves 30 and 32, as well as a selected length of main gown 22, may hang vertically as shown. When gown 10 is placed on surface 88 in this manner, the operator will preferably prefold flaps 26 and 28 back upon themselves in the manner shown in FIG. 3A.
Referring now also to FIG. 6, platen surface 88 is reciprocatively movable against a fixed frame 90. For example, one or more fluid cylinders, such as cylinder 92, may be provided for reciprocatively moving platen surface 88 to and from a location adjacent an intake of sleeve-tucking section 82. Toward this end, platen surface 88 may include rollers or the like which roll upon an underlying track defined in fixed frame 90. Any appropriate means may be provided to permit selective activation of the fluid cylinders by the operator. For example, presently preferred embodiments utilize an electric eye arrangement whereby the operator's hand is waved to activate the fluid cylinders.
As can be seen, sleeve-tucking section 82 includes a dead plate 94 having a width approximately the same as main gown 22. An endless conveyor 96 is positioned overlying and slightly spaced from dead plate 94 to engage and move gown 10 therealong. When gown 10 is delivered to sleeve-tucking section by the reciprocative movement of platen surface 88, the initial transverse fold (as shown in FIG. 3B) is automatically produced by the nip between dead plate 94 and conveyor 96.
The operation of sleeve-tucking section 82 is shown in FIGS. 7A and 7B. A pair of sleeve-tuckers 98 and 100 are located beside the opposite lateral sides of dead plate 94. As shown particularly in FIG. 7B, sleeve-tuckers 98 and 100 movably engage respective sleeves 30 and 32. As a result, sleeves 30 and 32 are folded behind dead plate 94 in the manner illustrated in FIG. 3C.
Sleeve tuckers 98 and 100 comprise respective longitudinal elements situated in parallel to dead plate 94 and movable in a direction transverse thereto. For example, sleeve tucker 98 includes a longitudinal rod 102 pivotally connected to a four-bar linkage 104, which is itself pivotally connected to the fixed frame. A fluid cylinder 106 is also pivotally connected to four-bar linkage 104 to cause the transverse movement of rod 102 at the desired time. An electric eye or other suitable activation means may be employed to detect the position of gown 10 and initiate activation of fluid cylinder 106. It can be seen that sleeve-tucker 100 is similarly constructed, comprising longitudinal rod 108, four-bar linkage 110 and fluid cylinder 112.
As will now be described with reference to FIGS. 8A through 8C, longitudinal folding section 84 functions to fold gown 10 along longitudinal fold lines as illustrated in FIG. 3E. Toward this end, longitudinal folding section 84 includes a dead plate 114 underlying an endless conveyor 116. It will be noted that the width of dead plate 114 is considerably less than dead plate 94 to allow the longitudinal folds produced in this section.
A pair of fixed guide rods 118 and 120 are located adjacent lateral sides of dead plate 114 near the output of sleeve-tucking section 82. In addition, longitudinal folding section 84 further includes a pair of fixed folding plates 122 and 124 located below dead plate 114. As shown, right folding plate 122 is situated slightly ahead of left folding plate 124 in the product stream. As the leading plate, right folding plate 122 will preferably be located slightly above left folding plate 124.
As can be seen in FIG. 8A, gown 10 first engages guide rods 118 and 120 as it is received on dead plate 114 from the output of sleeve-tucking section 82. The slope of guide rods 118 and 120 thus begins the desired longitudinal folds about dead plate 114. Next, as shown in FIG. 8B, the depending flaps formed in this manner engage the angled leading faces of folding plates 122 and 124. As a result, the flaps are folded behind dead plate 114 in the desired manner, as illustrated in FIG. 8C.
Referring now to FIG. 9, the garment then proceeds to transverse folding section 86. In this case, transverse folding section 86 includes respective folding mechanisms 126 and 128 for sequentially producing a pair of transverse folds. As shown, folding mechanisms 126 and 128 are opposed by a relatively lengthy overhead conveyor 130. A delivery conveyor 132 is also provided to move the garment to a support element 134 at the output end of the overall apparatus.
As can be seen, folding mechanism 126 includes a plurality of endless belts 136 extending about three rollers 138, 140 and 142 in a triangular arrangement. A fluid-actuated engaging mechanism 144 is located inside of the triangular structure to engage the garment along a first transverse fold line as will be explained below. Referring now also to FIG. 9A, engaging mechanism 144 comprises a base bar 146 having a plurality of finger members 148 attached thereto. Finger members 148 are located to extend between adjacent belts 136 when engaging mechanism 144 is activated.
Folding mechanism 128 similarly includes a plurality of endless belts 150. In this case, however, belts 150 extend about four rollers 152, 154 156 and 158 in a parallelogram arrangement. A fluid-actuated engaging mechanism 160, similar in its construction to engaging mechanism 144, is located inside of the parallelogram structure to engage the garment along a second transverse fold line.
As can be clearly seen in FIGS. 10A through 10E, the triangular structure of folding mechanism 126 provides a downslope 162 in the garment travel path. A nip 164, formed between overhead conveyor 130 and folding mechanism 128, is located opposite downslope 162 in alignment with engaging mechanism 144. Similarly, folding mechanism 128 provides a downslope 166 and an opposing nip 168. Nip 168 is formed between overhead conveyor 130 and delivery conveyor 132.
As shown in FIGS. 10A and 10B, the garment is carried from dead plate 114 into a nip 170 defined between roller 140 and an opposed roller 172 about which overhead conveyor 130 extends. The garment then proceeds along downslope 162, until engaging mechanism 144 is activated as shown in FIG. 10C. As a result, the garment will be inserted into nip 164 along the first transverse fold line.
In presently preferred embodiments, activation of engaging mechanism 144 may be effected utilizing a suitable electric eye arrangement. For example, an electric eye may be located adjacent nip 170 to detect when a leading edge of the garment has passed. Suitable delay circuitry can then activate engaging mechanism at the appropriate time.
As illustrated in FIG. 10D, the garment next proceeds along the top of folding mechanism 128 and subsequently along downslope 166. At a predetermined time, engaging mechanism 160 will be activated as shown in FIG. 10E. As a result, the garment will be forced into nip 168 along the second longitudinal fold line. Like engaging mechanism 144, engaging mechanism 160 can be activated in this manner utilizing an electric eye and appropriate time delay circuitry. This electric eye can be located, for example, along the top of folding mechanism 128.
As shown in FIG. 11, the garment is then passed to support element 134 by delivery conveyor 132. At this stage, the garment will be fully folded except for the central longitudinal fold illustrated in FIG. 3H. As shown in FIG. 12, support element 134 may include a longitudinal rod 172 about which this final fold can be easily made by the machine operator.
It can be seen that the present invention provides a surgical gown in an improved folded arrangement, as well as methods and apparatus for producing same. While preferred embodiments and preferred methodology have been shown and described, modifications and variations may be made thereto. For example, the sleeves may be tucked manually at the input of a garment folding apparatus, thus eliminating the need to provide an automated sleeve-tucking section.
One of skill in the art will appreciate that these and other modifications and variations are included within the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the invention may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to be limitative of the invention so further described in such appended claims.
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A surgical gown in an improved folded arrangement, as well as methods and apparatus for producing same. Like prior art book-folds, the folded arrangement includes left and right hand pockets to facilitate aseptic donning by a medical professional. Unlike prior art book-folds, however the folded arrangement of the invention employs a unique fold sequence particularly amenable to automated processing. Methods of the invention are directed to the specific fold sequences that can be utilized to produce the folded arrangement. Apparatus for producing the folded arrangement includes a number of operative sections functionally arranged in series.
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BRIEF SUMMARY OF THE INVENTION
This invention relates to a non-surgical method and apparatus for relieving a substantial amount of work load on the heart muscle by withdrawing a continuous flow of blood from one input chamber and mechanically pumping it directly into an output chamber, such as the pumping from the right ventricle directly into the pulmonary artery.
Heart failure following acute myocardial infraction, valvular diseases, unsuccessful coronary balloon angioplasty, or even after open-heart procedure is primarily due to markedly decreased performance of the heart muscle. It is the purpose of the apparatus and procedure to be described herein to provide normal or even increased coronary circulation in a nonambulatory patient while reducing the work load on the heart pump by 20% or more. It is believed that, unless seriously damaged, the heart of an adequately anticoagulated hospitalized patient operating at such a reduced work load will completely rebuild its strength within several days thus obviating the need for surgical treatment, possible further deterioration and death.
Many ventricular assist devices have been developed, many of which were designed to relieve the ventricle of its work load and to enhance coronary circulation. Most of these ventricular assist devices, such as the intra-aortic balloon pump, the archimedes pump and others are limited to assist only the left ventricle. In may instances, however, right ventricular failure may instigate the whole catastrophic event of heart failure.
During open heart surgery, the principle of venting the heart, especially the left ventricle, is a basic procedure. This technique requires a negligible amount of time and involves the insertion of additional cannula through the left atrium or pulmonary vein into the ventricle, through the left ventricular apex, or through the aortic root for preventing overdistention of a paralyzed heart.
In a compromised heart, following an acute myocardial infarction or a complicated open-heart operation, assisting the heart pump by decreasing its work load and increasing coronary circulation is the object of immediate therapeutic measures, either by drugs or mechanical devices. The ventricular venting loop (VVL) to be described provides as accessory pathway of cardiac output venting a fraction of the stroke volume continuously from the ventricle to the systemic circulation. In the case of right ventricular failure, the right ventricle is vented and the stroke volume is perfused back to pulmonary circulation. This venting loop is activated by a suitable pump, such as an electrically powered portable roller pump located near the patient.
The catheter in the ventricular venting loop (VVL) is introduced percutaneously by Seldinger technique into the femoral artery or vein. In left ventricular venting, the tip of a double-lumen catheter is advanced into the left ventricle while in right ventricular venting, the catheter tip with an inflated arterial balloon (as in the Swan-Ganz catheter) is allowed to flow with the blood stream to pass the right ventricle into the pulmonary artery. The catheter has spaced inflow and outflow ports that are coupled to silastic tubing wrapped around heads of the roller pump, the RPM of which can be regulated to provide a desired cardiac output.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings which illustrate the preferred embodiment of the invention:
FIG. 1 is a phantom anatomic view of a human body illustrating the general positioning and location of a right ventricular assist device extending between a roller pump and through the femoral vein to the pulmonary artery;
FIG. 2 is a similar view of a left ventricular assist device extending from a pump and through the femoral artery to the left ventricle;
FIG. 3 is an enlarged detailed view of the right ventricular assist device of FIG. 1;
FIG. 4 is a detailed drawing illustrating the outer lumen terminal in the right assist device;
FIG. 5 is a sectional view illustrating the crux which couples the roller pump to the coaxial tubing to the outer lumen terminal; and
FIG. 6 is an enlarged detailed view of the left ventricular assist device of FIG. 2.
DETAILED DESCRIPTION
It will be appreciated that it is highly unlikely that any treatment of a patient will require the application of both a left and right ventricular assist devices as shown in FIGS. 1 and 2. However, both devices and procedures are described and claimed in this single patent document since the methods of use are identical and, except for a flow direction within the arterial tubing and an arterial balloon in the right venting loop, the instruments themselves are identical.
As illustrated in FIG. 1, the right ventricular assist device includes a portable motor driven pump 10 having an fluid inlet 12 and fluid outlet 14. The pump is coupled to a double lumen or coaxial tubing 16 about thirty inches in length, the outer tubing of the coaxial pair terminating in an inflow terminal several inches short of an outflow terminal in the end of the inner tubing as shown in FIG. 3. As used herein, the terms "double lumen" and "concentric tubing" refer to a small diameter tubing within a larger tubing; there is no requirement that the tubes actually be concentric or coaxial. Surrounding the outflow terminal is a small 2 cc. balloon which may be inflated and deflated as required through a very small tubing coupled to a 2 cc. syringe 18. In use, the outflow terminal of this catheter with its balloon deflated is introduced into the femoral vein 19. The balloon is then inflated with air and the coaxial tubing is drawn with the venous blood flow into the right ventricle of the heart and the inner tubing continues into the pulmonary artery. Operation of the pump 10 then acts to withdraw blood from the right ventricle and return the same blood into the pulmonary artery thus forming a right ventricular venting loop that bypasses the pulmonic valve and relieves the heart muscle of a portion of its normal work load.
The left ventricular assist device of FIG. 2 is nearly identical with that of FIG. 1, the difference being that the catheter in the left ventricular assist device will be forced against the blood flow and therefore does not use an arterial balloon. In FIG. 2, the motor driven pump 10 coupled to the concentric tubing receives its inflow through the inner tubing of the concentric pair and outflows through the outer tubing. The catheter is introduced into the femoral artery and is passed into the aorta and continues into the left ventricle. Rotation of the pump 20 operates to withdraw arterial blood from the left ventricle into an inflow terminal in the end of the inner tubing of the concentric pair and return the same blood into the aorta from the outflow terminal at the end of the outer tubing, thus forming a left ventricular venting loop that bypasses the aortic valve to relieve the heart muscle of a portion of its normal work load.
FIG. 3 is a detailed drawing illustrating the right ventricular assist device of FIG. 1 and shows the approximate positions of the inflow and outflow terminals within the heart to provide an effective venting loop.
The pump 10 of FIG. 3 is preferably driven by an AC/DC (battery) motor for portability and, in the preferred embodiment, is a roller pump employing a silastic tubing 22 confined between an outer ring 24 and a plurality of rollers 26 extending from the surface of a disc rotated by the AC/DC motor. As the motor rotates the disc in a direction shown by the arrows 28, the rollers squeeze the tubing 22 and its fluid contents from the inlet 12 to the outlet 14.
The pump 10 is coupled to a crux 30, shown in detail in the sectional drawing of FIG. 5. The crux is a hard plastic, Y-shaped coupling which couples the pump inlet 12 to the outer conduit of the coaxial tubing 16 and the pump outlet 14 to the inner conduit of the tubing 16.
As previously noted, the outer tubing 32 of the coaxial pair has an approximate inside diameter of 5/16 inch and, in use, extends from the crux 30, through the femoral vein, up through inferior vena cava into the right atrium 32 and through the tricuspid valve 34 into the right ventricle 36 where it terminates in a soft perforated inflow terminal 38 shown in greater detail in FIG. 4. In the preferred embodiment the terminal 38 is formed of PVC, but may be formed of materials such as silicone or polyethylene.
The inflow terminal 38 of FIG.4 merely seals the end of the outer tubing 32 around the inner tubing 40 and a very small air conduit 42 so that venous blood drawn in by the inflow terminal 38 located in the right ventricle 36 will be passed by action of the pump 10 through the pump and will flow through the the inner tube 40 of the concentric pair and out through the outflow terminal 46 into the pulmonary artery 44.
The inner tubing 40 is a soft lumen having an inside diameter of about 1/8 inch and is coupled between the crux 30 and its outflow terminal which comprises a blunt end portion with perforations at and surrounding the tip. Approximately a half inch behind the tip of the outflow terminal is a small 2 cc. balloon 48 that is inflatable and deflatable through the small air conduit 42 that extends through the inflow terminal 38 and outer tubing 32 with the inner tubing 40 to the crux 30 and to a syringe 18.
In use, the terminal end of the concentric tubing is introduced by Seldinger technique into the femoral vein and the balloon 48 is inflated with air by the syringe 18. The catheter, carefully monitored, is drawn by the balloon in the venous blood flow toward the heart and passes the inferior vena cava, the right ventricle and into the pulmonary artery and is thus positioned so that the inflow terminal of the system in in the ventricle and outflow is in the artery. The pump 10, when activated, thus relieves the heart muscle of much of its work load and permits the heart muscle to relax while blood continues to flow at a normal or even greater rate, depending upon the rotational velocity of the roller pump 10.
FIG. 6 is a detailed view illustrating the left ventricular assist device which, as in the right ventricular loop, employs the motor driven pump 10 coupled to a crux 50 which draws fluid into the pump through the inner tubing 52 of a lumen pair which includes the outer tubing 54. It will be noted that this flow is opposite to that described in connection with FIG. 3 and this is represented in FIG. 6 by reversing the direction of the pump 10 as shown by the arrows 56. If desired, the motor 10 of FIG. 6 may be rotated in a direction identical as that in FIG. 3, and that the correct inflow and outflow to the pump may then be controlled by the design of crux employed.
In this embodiment, the catheter is inserted into the femoral artery and, while fluoroscopically monitored, is moved through the descending aorta 58 into the aorta 60 and thence through the aortic valve 62 into the left ventricle 64. The inflow terminal 66 is at the distal end of the inner tubing 52 and is positioned in the left ventricle 64 to withdraw arterial blood which is pumped by the pump 10 through the outer tubing 54 to its outflow terminal 68 in the aorta 60. The ventricular venting loop thus formed bypasses an important and possibly overworked muscle of the heart to enable that ventricle to be relieved of its work load while continuing normal or even enhanced circulation.
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A catheter and fluid pumping apparatus and the method for bypassing portions of the heart to temporarily reduce the work load on the heart muscle. A double tube catheter is introduced into the femoral vein or artery and is advanced into the ventricle where blood is drawn and mechanically pumped back into the heart at a position downstream, such as the aorta or the pulmonary artery. The desired cardiac circulation can be maintained while relieving the load on the heart muscle to enable it to rebuild its strength.
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FIELD OF THE INVENTION
The present invention relates to an improved wafer process tube apparatus and method for substantially normalizing and controlling gas flow rates in vertical furnaces (e.g., vertical heat treatment furnaces, vertical oxidation furnaces, and vertical diffusion furnaces) such as those used in the semiconductor production process, and more particularly to a process tube apparatus and method which can reduce in-plane variations and wafer to wafer variations in thickness and quality of thin films formed on semi-conductor wafers and of semi-conductor wafers annealed within such vertical furnaces.
DESCRIPTION OF BACKGROUND ART
FIG. 12 is a side view diagram by way of example, of a conventional process tube 1 for use in vertical furnaces.
The process tube 1 for vertical furnaces is of a quartz-made cylinder with its upper end closed and its lower end left open. A process gas introducing pipe 2 is connected to the center of an upper end portion of the process tube 1 for communication with an inner cavity of the process tube, and an exhaust pipe 3 is connected to a peripheral wall of the process tube 1 at a position near its lower end for communication with the tube's inner cavity through an exhaust port la formed at the same position.
A cap 4 is inserted into the lower open end of the process tube 1 for vertical furnaces while leaving an appropriate gap between itself and an inner circumferential surface of the process tube 1 for vertical furnaces. A wafer mount boat 5 is supported to an upper end surface 4a of the cap 4 directed toward the inner cavity of the process tube 1.
In other words, the cap 4 is supported at its lower end by a lifting device (not shown) and inserted into the process tube 1 for vertical furnaces from below, with the wafer mount boat 5 kept supported on the upper end surface 4a of the cap 4.
The cap 4 is inserted into the process tube 1 such that the upper end surface 4a is positioned above the exhaust port 1a. Thus, during the process carried out in the vertical furnace, the exhaust port 1a of the process tube 1 faces an outer circumferential surface 4b of the cap 4.
Accordingly, gas supplied to the process tube 1 via the process gas introducing pipe 2 flows downwardly and reaches the exhaust port 1a after passing the gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4, following which the gas is discharged to the exterior via the exhaust pipe 3.
In the above conventional process tube 1 for vertical furnaces, however, since the cap 4 is simply cylindrical in shape and the exhaust port 1a is defined at only one location in the circumferential direction, there occurs in the vicinity of the upper end surface 4a of the cap 4 a difference in exhaust rate between a region A near the exhaust port 1a and other regions remote therefrom. As a result, the temperature in the region A where the exhaust rate increases is more likely to be lower than in the other regions.
This has raised a problem that in-plane variations and wafer to wafer variations in thickness and quality of thin films formed near the cap 4 inside the vertical furnace, and of wafers annealed at that location may become significant.
To overcome the above problem, prior systems have attempted to carry out the process while rotating the cap 4 within the process tube 1 for vertical furnaces. However, this method is accompanied by a high risk that the inner cavity of the process tube 1 may become contaminated by dust or dirt which is produced due to the presence of sliding parts in the process tube 1.
Another approach which has been used is the connection of a plurality of exhaust pipes 3 to the process tube 1 for vertical furnaces so that the exhaust flow will not be localized. However, this method raises the problem that the layout of the apparatus around the process tube 1 is complicated or because of the complication layout, the layout must be changed.
SUMMARY OF THE INVENTION
The present invention has been made to overcome the above-mentioned problems in the prior art, and its object is to provide a wafer process tube for vertical furnaces which can reduce in-plane variations and wafer to wafer variations in thickness and quality of thin films formed on wafers in the vertical furnaces, and of wafers annealed therein, by normalizing the gas flow rate within the process tube.
In accordance with one embodiment of the invention, a cap of heat insulating material is inserted into the vertical process tube with the upper surface of the cap being higher than the exhaust port of the tube. A groove of appropriate dimensions is formed around the outer circumferential surface of the cap in close proximity to the exhaust port of the tube. The flow resistance of the groove is lower than that of the gap between the inner wall of the process tube and the outer wall of the cap near the exhaust port of the tube. The flow resistance of the groove gradually increases, however, in proceeding circumferentially one hundred eighty (180) degrees about the cap from a position in close proximity with the exhaust port of the tube. Gas introduced into the process tube flows at a uniform rate between the inner circumference of the tube and the outer circumference of the cap to the exhaust port. Temperature variations caused from non-uniform gas flow rates thereby are prevented, and in-plane variations and wafer to water variations in thickness and quality of thin films formed on wafers and of wafers annealed may be controlled.
In another embodiment of the invention, the groove about the circumference of the cap is inclined such that the distance between the groove and the upper end surface of the cap gradually decreases in proceeding one hundred eighty (180) degrees about the outer circumference of the cap from a position in close proximity with the process tube exhaust port. The flow resistance between the tube and cap becomes smaller, while the flow resistance of the groove increases in proceeding one hundred eighty degrees along the groove from a position in close proximity to the exhaust port.
In yet another embodiment of the invention, an inclined ring of heat insulating material is fixed to the outer circumferential surface of the cap at a position higher than the exhaust port of the process tube, such that the distance between the ring and the upper face of the cap gradually decreases in proceeding one hundred eighty (180) degrees along the outer circumference of the cap from a position in close proximity with the exhaust port of the process tube. As gas flows from the top of the process tube downward between the inner wall of the tube and the outer wall of the cap toward the exhaust port of the tube, a high pressure region is formed above the ring, and a low pressure region is formed below the ring to normalize the rate of gas flow within the process tube.
In still another embodiment of the invention, a horizontal ring with a plurality of cutouts is fixed about the outer circumferential surface of the cap above the exhaust port of the process tube and near the upper end surface of the cap. The circumferential distance between ring cutouts gradually decreases in proceeding one hundred eighty (180) degrees about the outer circumference of the cap from a position in close proximity with the exhaust port of the process tube. In one alternative, the circumferential distance between cutouts may be held constant while the cross-sectional area of the cutouts is gradually increased in proceeding one hundred eighty (180) degrees about the circumference of the cap from a position in close proximity with the exhaust port of the process tube. In another alternative, a ring without cutouts has a vertical height which gradually decreases in proceeding one hundred eighty degrees about the ring from a position in closest proximity to the exhaust port. In a further alternative, a ring without cutouts has a horizontal width which gradually decreases in proceeding one hundred eighty degrees about the ring from a position in closest proximity to the exhaust port.
As gas flows from the top of the process tube downward between the inner wall of the process tube and the outer wall of the cap to the exhaust port of the tube, the gap between the ring and the inner surface of the process tube creates a gradually decreasing flow resistance in proceeding one hundred eighty (180) degrees about the circumference of the cap from a position in close proximity with the exhaust port. The gas flow rate thereby is normalized and temperature variations causing unacceptable in-plane wafer and wafer to wafer are avoided.
In a further embodiment, a passage is formed inside of the cap, with one end open at the center of the upper end surface of the cap, and the other end open to the outer circumferential surface of the cap at a position facing the exhaust port of the process tube. The passage includes a cavity near its upper end which acts as a buffer. By making the flow resistance of the passage less than the flow resistance encountered between the inner process tube wall and the outer cap wall, most gas flow to the exhaust port occurs through the passage. Variations in gas flow rates about the outer surfaces of the cap thereby are substantially reduced.
In yet a further embodiment of the invention, a horizontal, hollow annular ring is hermetically sealed about an outer circumferential surface of the process tube, and is physically connected to an exhaust port. Communication holes at equal circumferential distances apart are formed in the wall of the process tube, and in alignment with the annular pipe, to allow gas to pass from the interior of the process tube through the annular ring to the exhaust port. The cross-sectional area of the communication holes gradually increase in proceeding one hundred eighty degrees about the ring from a position in close proximity to the exhaust port. In the alternative, the plurality of communication holes in the above embodiment may be formed to have a gradually decreasing circumferential distance therebetween in proceeding circumferentially about the process tube from a position where the exhaust port of the tube is connected to the annular pipe. The cross-sectional area of the communication holes in this instance, however, remain equal in proceeding circumferentially from a position in closest proximity to the exhaust port. Flow resistance from the interior of the process tube through the communication holes to the annular ring thus decreases, while the flow resistance within the annular ring increases, in proceeding circumferentially one hundred eighty (180) degrees about the pipe from the exhaust port. The flow rate of gas circumferentially about the cap thereby is normalized.
For a better understanding of the present invention, reference may be had to the accompanying drawings wherein the same reference numbers have been applied to like parts.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view, partially sectioned, showing the construction of a first embodiment of the present invention.
FIG. 2 is a top plan view of a cap in the first embodiment of the present invention.
FIG. 3 is a side view, partially sectioned, showing the construction of a second embodiment of the present invention.
FIG. 4 is a side view, partially sectioned, showing the construction of a third embodiment of the present invention. 10 FIG. 5 is a top plan view of a cap in the third embodiment of the present invention.
FIG. 6 is a side view, partially sectioned, showing the construction of a fourth embodiment of the present invention.
FIG. 7 is a top plan view, partially sectioned, showing the construction of a fourth embodiment of the present invention.
FIG. 8 is a side view, partially sectioned, showing the construction of a fifth embodiment of the present invention.
FIG. 9 is a top plan view, partially sectioned, of a cap in the fifth embodiment of the present invention.
FIG. 10 is a side view, partially sectioned, showing the construction of a sixth embodiment of the present invention.
FIG. 11 is a sectional view taken along line I--I in FIG. 10.
FIG. 12 is a side view diagram of a prior art process tube used in vertical furnaces.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred embodiments of the present invention will be described below with reference to the drawings.
FIRST EMBODIMENT OF INVENTION
FIG. 1 shows a first embodiment of the present invention; i.e., it is a side view, partially sectioned, showing a condition that a cap 4 containing heat insulating material such as glass wool therein is inserted into an opening of a quartz-made, cylindrical process tube 1 for vertical furnaces at its lower end or bottom.
The construction of this embodiment will first be described.
An exhaust pipe 3 is connected to a peripheral wall of the process tube 1 at a position near the bottom opening for communication with an inner cavity of the tube through an exhaust port 1a formed at the same position. The cap 4 is inserted into the process tube 1 such that an upper end surface 4a of the cap 4 directed toward the inner cavity of the process tube 1 is positioned above the exhaust port 1a.
Thus, the exhaust port 1a faces an outer circumferential surface 4b of the cap 4.
Between a flange 1b formed to continuously outwardly project from the lower end of the process tube 1 and a flange 4c formed to continuously outwardly project from the lower end of the cap 4, there is interposed a ring-shaped sealing member 4d fixed to an upper surface of the flange 4c, thereby keeping air tightness. Additionally, as with the conventional cap shown in FIG. 12, a wafer mount boat is supported on the upper end surface 4a of cap 4.
Then, a groove 6 serving as exhaust flow uniformalizing or normalizing means is formed in the outer circumferential surface 4b of the cap 4.
As shown in the side view of FIG. 1 and the top plan view of FIG. 2, the groove 6 is of a groove defined continuously in the circumferential direction at the same level as the exhaust port 1a, and is formed by recessing the outer circumferential surface 4b of the cap 4 into a semicircular shape in cross-section. It is preferable that the cross-sectional area of flow passage defined by the groove 6 is comparable to or greater than that defined by the exhaust pipe 3.
Operation of this embodiment will now be described. Gas supplied to the process tube 1 flows downwardly and reaches the exhaust port 1a after passing the gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4, following which the gas is discharged to the exterior via the exhaust pipe 3.
With this embodiment, the groove 6 formed in the outer circumferential surface 4b of the cap 4 is positioned at the same level as the exhaust port 1a in opposite relation thereto, and the cross-sectional area of flow passage defined by the groove 6 is set to be relatively large.
The flow resistance of the groove is lower than that of the gap between the inner wall of the process tube and the outer wall of the cap near the exhaust port of the tube. The flow resistance of the groove gradually increases, however, in proceeding circumferentially one hundred eighty degrees about the cap from a position in close proximity to the exhaust port of the tube 1.
Therefore, the flow passage defined by the gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4 is subjected to substantially the same conditions around the entire circumference of the cap 4. As a result, the exhaust flow is permitted to uniformly flow into the entire gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4, whereby the exhaust flow is prevented from localizing.
Consequently, the localized temperature drop which has heretofore caused in-plane variations and wafer to wafer variations in quality of wafers located near the cap 4 can be prevented to improve yield of wafers.
In addition, since the construction of this embodiment only requires it to form the groove 6 in the outer circumferential surface 4b of the cap 4, a substantial increase in cost will not occur, and there is no need of changing the layout around the process tube 1, making the present invention easily adapted to existing equipment.
Furthermore, since there is no need of providing an additional rotating mechanism or the like, any risk of the inner cavity of the process tube 1 being contaminated by dust or dirt produced due to the presence of such a mechanism, will be avoided.
SECOND EMBODIMENT OF INVENTION
FIG. 3 shows a second embodiment of the present invention. It should be noted that certain elements of FIG. 3 correspond to those of FIG. 1 which illustrate the first embodiment, and those members and locations which are identical to those in FIG. 1 are denoted by the same reference numerals and their description already given above will not be repeated.
In this embodiment, the groove 6 formed as an exhaust flow uniformalizing or normalizing means in the outer circumferential surface 4b of the cap 4 is of a groove inclined such that the distance between itself and the upper end surface 4a of the cap 4 is gradually shortened as the groove spaces from the position facing the exhaust port 1a toward the opposite side in the circumferential direction.
To completely eliminate localization of the exhaust flow in the above construction of the first embodiment, the cross-sectional area of flow passage defined by the groove 6 is required to be so extremely large that flow resistance of the groove 6 can be perfectly ignored. In practice, therefore, there is a fear that the exhaust flow may be localized due to the flow resistance of the groove 6.
In this embodiment, however, since the groove 6 is inclined as mentioned above, the flow passage defined by the gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4 becomes shorter as it spaces from the position facing the exhaust port 1a.
Stated otherwise, by so inclining the groove 6, the flow passage leading from the inner cavity of the process tube 1 above the upper end surface 4a of the cap 4 to the groove 6 formed in the outer circumferential surface 4b of the cap 4 has flow resistance which becomes smaller as it spaces from the position facing the exhaust port 1a toward the opposite side in the circumferential direction, conversely to the flow resistance of the groove 6 itself. Therefore, by selecting an angle of inclination of the groove 6, the entire flow passage leading from the inner cavity of the process tube 1 to the exhaust port 1a is made uniform in flow resistance at any circumferential positions around the cap 4.
As a result, the exhaust flow in the process tube 1 is permitted to uniformly flow into the entire gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4, whereby the exhaust flow is reliably prevented from localizing.
The other operation and advantages of this embodiment are similar to those of the above first embodiment.
THIRD EMBODIMENT OF INVENTION
FIGS. 4 and 5 show a third embodiment of the present invention. It should be noted that those members and locations which are identical to those in the above first and second embodiments are denoted by the same reference numerals, and their description already given above will not be repeated.
In this embodiment, a ring 7 serving as exhaust flow uniformalizing or normalizing means is fixed to the outer circumferential surface 4b of the cap 4. The ring 7 is fixed to the outer circumferential surface 4b of the cap 4 at a position higher than the exhaust port 1a such that the distance between itself and the upper end surface 4a of the cap 4 is gradually shortened as the ring spaces from the position facing the exhaust port 1a toward the opposite side in the circumferential direction.
With such an arrangement, the gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4 essentially functions as an orifice, so that a region under higher pressure is formed above the ring 7 and a region under lower pressure is formed below it.
Then, since the ring 7 is fixed in such a manner as to make shorter the distance between itself and the upper end surface 4a of the cap 4 as it spaces from the position facing the exhaust port 1a, the lower-pressure region is located nearer to the inner cavity of the process tube 1 at a position remoter from the exhaust port 1a, causing the exhaust flow to more easily flow into the gap. Therefore, the entire flow passage leading from the inner cavity of the process tube 1 to the exhaust port 1a is made uniform in flow resistance at any circumferential positions around the cap 4.
As a result, the exhaust flow in the process tube 1 is permitted to uniformly flow into the entire gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4, whereby the exhaust flow is prevented from localizing.
The other operation and advantages of this embodiment are similar to as those of the above first embodiment.
FOURTH EMBODIMENT OF INVENTION
FIGS. 6 and 7 show a fourth embodiment of the present invention. It should be noted that those members and locations which are identical to those in the above first, second and third embodiments are denoted by the same reference numerals and their description already given above will not be repeated.
In this embodiment, a ring 7 is used as an exhaust flow uniformalizing or normalizing means similarly to the above third embodiment, but the ring 7 is horizontally fixed at a position higher than the exhaust port 1a.
The ring 7 has a plurality of cutouts 7a, . . . , 7a formed therein such that the interval between these cutouts is gradually shortened as the ring spaces from the position facing the exhaust port 1a toward the opposite side in the circumferential direction.
With such an arrangement, a region under higher pressure is formed above the ring 7 and a region under lower pressure is formed below it, as with the above third embodiment. In addition, since the cutouts 7a, . . . , 7a are formed at the positions as explained above, the gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4 has flow resistance which becomes smaller as it spaces from the position facing the exhaust port 1a toward the opposite side in the circumferential direction, causing the exhaust flow to more easily flow into the gap at locations remoter from the exhaust port 1a.
Therefore, the entire flow passage leading from the inner cavity of the process tube 1 to the exhaust port 1a is made uniform in flow resistance at any circumferential positions around the cap 4. As a result, the exhaust flow in the process tube 1 is permitted to uniformly flow into the entire gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4, whereby the exhaust flow is prevented from localizing.
While, in this embodiment, the gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4 is made to have smaller flow resistance as it spaces from the position facing the exhaust port 1a toward the opposite side in the circumferential direction, by forming the plurality of cutouts 7a, . . . , 7a in the ring such that the interval between these cutouts is gradually shortened as the cutout spaces from the position facing the exhaust port 1a toward the opposite side in the circumferential direction, the arrangement for making smaller the flow resistance of the aforesaid gap with the increasing distance from the exhaust port 1a is not limited to that of the illustrated embodiment. For example, the plurality of cutouts 7a, . . . , 7a may be formed in the ring 7 such that the interval between these cutouts 7a, . . . , 7a is set to be constant, but the opening area of the cutouts is gradually enlarged as the cutout spaces from the position facing the exhaust port 1a toward the opposite side in the circumferential direction. Alternatively, the ring 7 may be formed to have a smaller thickness or a narrower width as it spaces from the position facing the exhaust port 1a toward the opposite side in the circumferential direction.
The other operation and advantages of this embodiment are similar to those of the above first embodiment.
FIFTH EMBODIMENT OF INVENTION
FIGS. 8 and 9 show a fifth embodiment of the present invention. It should be noted that those members and locations which are identical to those in the above embodiments are denoted by the same reference numerals, and their description already given above will not be repeated.
In this embodiment, a passage 8 is formed as exhaust flow uniformalizing means in the cap 4. The passage 8 has one end being open in the upper end surface 4a of the cap 4 at the center thereof, and the other end being open in the outer circumferential surface 4b of the cap 4 at a position facing the exhaust port 1a.
Additionally, the passage 8 has a cavity portion 8a, of which diameter is larger than the other portion, near its opening in the upper end surface 4a.
With such an arrangement, by setting the flow resistance of the passage 8 to be smaller than that of the gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4, most of the exhaust flow is forced to reach the exhaust port 1a through the passage 8 opening at the center of the upper end surface 4a, whereby the exhaust flow is prevented from localizing.
Further, in this embodiment, the cavity portion 8a is defined midway the passage 8 near its upstream end to serve as a buffer. Therefore, the region where the exhaust rate is rapidly increased exists inside the cap, which is effective to make smaller in-plane variations and wafer to wafer variations in quality of wafers and so on.
The position where the one end of the passage 8 opens in the upper end surface 4a is not limited to the center of the upper end surface 4a. Alternatively, the passage 8 may open in a scattered patter over the upper end surface 4a.
The other operation and advantages of this embodiment are similar to those of the above first embodiment.
SIXTH EMBODIMENT OF INVENTION
FIGS. 10 and 11 show a sixth embodiment of the present invention. FIG. 10 is a side view, partially sectioned, showing the vicinity of the exhaust end of the process tube 1, and FIG. 11 is a sectional view taken along line I--I of FIG. 10. It should be noted that those members and locations which are identical to those in the above embodiments are denoted by the same reference numerals, and their description already given above will not be repeated.
In this embodiment, the process tube 1 is formed into a horizontal, double-wall tube or hollow annular ring in a part of the outer circumferential surface near its exhaust end, thereby forming an annular ring 9 which surrounds an axially central portion of the outer circumferential surface 4b of the cap 4.
The annular ring 9 is connected to the exhaust pipe 3 at one location in the circumferential direction for communication therebetween.
Further, the interior of the annular ring 9 is communicated with the inner cavity of the process tube 1 via six communication holes 10a to 10f.
These communication holes 10a to 10f are formed at six locations with a constant interval in the circumferential direction starting from the position facing the exhaust pipe 3. More specifically, of the communication holes 10a to 10f, the communication hole 10a formed at the position facing the exhaust pipe 3 has a minimum opening area. With the increasing distance from the exhaust pipe 3 in the circumferential direction, the opening area of the remaining communication holes becomes larger in the order of 10b, 10c and 10d, 10e on the opposite sides. The communication hole 10f formed at the position angularly spaced 180 degrees from the position facing the exhaust pipe 3 has a maximum opening area.
Therefore, the area through which the process tube 1 and the annular ring 9 are communicated with each other is increased as the annular ring spaces from the position, where the exhaust pipe 3 is connected to the annular ring 9, toward the opposite side in the circumferential direction.
Operation of this embodiment will now be described.
Gas supplied to the process tube 1 through the process gas introducing pipe 2 flows downwardly and reaches the annular ring 9 after passing the gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4 and the communication holes 10a to 10f, following which the gas is discharged to the exterior via the exhaust pipe 3.
As a result of selecting the opening areas of the communication holes 10a to 10f as explained above, the area. through which the process tube 1 and the annular ring 9 are communicated with each other is increased at the locations remoter from the exhaust pipe 3 and, therefore, the flow passage leading from inner cavity of the process tube 1 to the interior of the annular ring 9 has smaller flow resistance at the locations remoter from the exhaust pipe 3.
On the other hand, the flow resistance of the annular ring 9 between an arbitrary circumferential position thereof and the position where it is connected to the exhaust pipe 3, is larger at the locations remoter from the exhaust pipe 3 because that flow resistance is in proportion to the distance from the position where the annular ring 9 is connected to the exhaust pipe 3.
Stated otherwise, the flow resistance of the communication holes 10a to 10f and the flow resistance of the annular ring 9 itself exhibit characteristics reversed to each other, taking as a variable the distance from the position where the annular ring 9 is connected to the exhaust pipe 3. Thus, by appropriately selecting the opening areas of the communication holes 10a to 10f and the passage diameter of the annular ring 9, the entire flow passage leading from the inner cavity of the process tube 1 to the exhaust pipe 3 is made uniform in flow resistance at any circumferential positions around the cap 4.
As a result, the exhaust flow in the process tube 1 is permitted to uniformly flow into the entire gap between the inner circumferential surface of the process tube 1 and the outer circumferential surface 4b of the cap 4, whereby the exhaust flow is prevented from localizing.
Consequently, the localized temperature drop which has heretofore caused in-plane variations and wafer to wafer variations in thickness of thin films formed on wafers near the cap 4 and the thickness of wafers annealed near cap 4 can be prevented to improve yield of wafers.
In addition, since the construction of this embodiment only requires it to modify the configuration of peripheral wall of the conventional process tube 1 near its exhaust side end, a substantial increase in the cost will not result, and there is no need of changing the apparatus layout around the process tube 1, making the present invention easily adaptable to existing equipment.
Furthermore, since there is no need for providing an additional rotating mechanism or the like, any risk that the inner cavity of the process tube 1 may be contaminated by dust or dirt produced due to the presence of such a rotating mechanism is eliminated.
While, in this embodiment, the area through which the process tube 1 and the annular ring 9 are communicated with each other is gradually increased as the annular ring spaces in the circumferential direction from the position where the exhaust pipe 3 is connected to the annular ring 9, by selecting the opening areas of the communication holes 10a to 10f formed with a constant interval to become larger at the locations remoter from the exhaust pipe 3, the construction for making that communication area larger at the locations remoter from the exhaust pipe 3 is not limited to the illustrated embodiment. For example, the inner cavity of the process tube 1 may be communicated with the annular ring 9 through a plurality of communication holes formed such that the interval between these communication holes is narrowed as the annular ring spaces in the circumferential direction from the position where the exhaust pipe 3 is connected to the annular ring 9. In this instance, however, the cross-sectional areas of the communication holes remain equal in proceeding about the ring.
As an example of experiments conducted in creating the above embodiments, a vertical furnace which has the process tube 1 according to the above second embodiment of the present invention was used, and an oxide film was formed all over the surface of an 8-inch wafer by setting a target thickness to 12 nm. As a result, variations in thickness of the oxide film in the wafer plane could be held down in the range of 3 to 2% in contrast with the range of 5 to 3% in the prior art. Also, variations in thickness of the oxide film from wafer to wafer could be held down in the range of 3 to 2% in contrast with the range of 5 to 3% in the prior art. Consequently, yield of wafers was improved 10% in comparison with the case using the prior art vertical furnace.
It should be noted that the above variations in thickness of the oxide film was calculated from the following formula: ##EQU1##
According to the present invention, as fully described above, there can be obtained advantages that the exhaust flow in the process tube for vertical furnaces is prevented from localizing and, as a result, in-plane variations and wafer to wafer variations in thickness and quality of wafers subjected to film forming and annealing are reduced.
In support of the semi-conductor wafer claims of this application, we refer and incorporate by reference the wafer structural teachings of S. M. Sze as set forth in the book entitled "Physics of Semiconductor Devices", second edition, Wiley-Interscience, with 1981 Copyright.
While there has been illustrated and described what is at present considered to be the preferred embodiments of the present invention, it will be appreciated that numerous changes and modifications are likely to occur to those skilled in the art, and it is intended to cover in the appended claims all those changes and modifications which fall within the true spirit and scope of the present invention.
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A cap inserted into a wafer process tube for vertical furnaces is provided with exhaust flow normalizing means which can control or prevent variations in exhaust flow rates in the process tube, and thereby control variations in thickness of wafers subjected to film forming and annealing.
In the alternative, an annular hollow ring is hermetically sealed around an outer circumferential surface of the process tube. An exhaust pipe is connected to the hollow annular ring. Gas communication holes are formed in the wall of the process tube to accommodate the flow of gas between the tube and the hollow annular ring. The spacing and cross-sectional area of the communication holes are such as to equalize flow resistance circumferentially around the cap. In-plane variations and wafer to wafer variations in thickness and quality of wafers subjected to film forming and annealing thereby are reduced and controlled.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to methods and systems for material treatment, such as particulate size reduction. Particularly, the present invention is directed to methods and systems for material size reduction that are useful in coal technology.
[0003] 2. Description of Related Art
[0004] In operations that use coal for fuel, finely-ground coal particles or “fines” are required for efficient operation, yielding higher combustion efficiency than stoker firing, as well as rapid response to load changes. Using coal fines for combustion has the potential for less nitrous oxide (NO x ) emissions and keeps oversized loss-on-ignition (LOI) unburned coal particles from contaminating the marketable ash byproduct of the combustion chamber. Thus, it is common practice to supply raw coal to a device, such as a pulverizer, that will reduce the size of the coal to particles within a desirable size range prior to being conveyed to the furnace for combustion.
[0005] Many pulverizers employ systems and methods including one or more crushing and grinding stages for breaking up the raw coal. Coal particles are reduced by the repeated crushing action of rolling or flailing elements to dust fine enough to become airborne in an air stream swept through the pulverizer. The dust particles are entrained in the air stream and carried out for combustion.
[0006] It should be readily apparent that the process of reducing solid coal to acceptably sized fines requires equipment of high strength and durability. Therefore, there exists a continuing need for crushing and grinding components which can reduce solid coal to acceptably sized fines in less time with greater efficiency, and in a manner which results increased wear life for those components. The present invention provides a solution for these problems.
SUMMARY OF THE INVENTION
[0007] The purpose and advantages of the present invention will be set forth in and become apparent from the description that follows. Additional advantages of the invention will be realized and attained by the methods and systems particularly pointed out in the written description and claims hereof, as well as from the appended drawings.
[0008] To achieve these and other advantages and in accordance with the purpose of the invention, as embodied herein, the invention includes a swing hammer for fastening on a crusher rotor assembly or wheel of a material size reducing and drying system. The crusher rotor assembly is preferably mounted on a center shaft of the system, wherein the center shaft defines an axis of rotation and is configured for rotational motion within a process chamber of the material size reducing system.
[0009] In accordance with one embodiment of the invention, the swing hammer is made at least in part from a ductile impact absorbing backing material defining a hammer face. Preferably, a wear resistant material is bonded to the hammer, such as to the hammer face. The backing material absorbs impact for the wear resistant material. The wear resistant material can take on a variety of forms, such as a wear pad that is formed separately and bonded to the hammer face, among others. The wear resistant material protects the softer backing material from wear during the crushing and/or drying process.
[0010] The hammer can be made in a variety of ways. Preferably, the hammer is made by way of a forging operation. The hammer is preferably shaped so that it fits over and within a lug on the crusher rotor. The crusher rotor may be fastened to the rotating assembly by way of a crusher rotor spacer. Both the crusher rotor and hammer may have the same size hole drilled through them. The hammer preferably has two holes per lug and the crusher rotor preferably has one hole per lug. In accordance with one embodiment, the swing hammer of the invention is attached to the crusher rotor by way of a hammer pin. The hammer pin may be held in place, for example, by a cotter pin positioned in a hole on the crusher rotor lug.
[0011] It is to be understood that both the foregoing general description and the following detailed description are exemplary and are intended to provide further explanation of the invention claimed.
[0012] The accompanying drawings, which are incorporated in and constitute part of this specification, are included to illustrate and provide a further understanding of the method and system of the invention. Together with the description, the drawings serve to explain the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] So that those having ordinary skill in the art to which the present invention pertains will more readily understand how to make and use the present invention, an embodiment thereof will be described in detail with reference to the drawings, wherein:
[0014] FIG. 1 is a front view of an exemplary rotary coal pulverizer (duplex model) which can employ a plurality of swing hammers constructed in accordance with the present invention mounted therein.
[0015] FIG. 2 is a side view of the rotary coal pulverizer of FIG. 1 , illustrating the discharge from the fan section of the pulverizer.
[0016] FIG. 3 is an enlarged localized partial cross-sectional view of a portion of the exemplary rotary coal pulverizer of FIG. 1 , illustrating a prior art swing hammer positioned on the wheel assembly in the crusher section.
[0017] FIGS. 4(A)-4(B) depict a first embodiment of a two-piece prior art swing hammer with a guard.
[0018] FIG. 5 depicts a second embodiment of a one-piece prior art swing hammer without a guard.
[0019] FIGS. 6(A)-6(C) depict perspective, front and side views of a first representative embodiment of a swing hammer made in accordance with the invention, respectively.
[0020] FIG. 7 depicts wear performance of the prior art swing hammer depicted in FIGS. 4(A)-4(B) , using a template.
[0021] FIG. 8 depicts wear performance of the swing hammer made in accordance with the invention depicted in FIGS. 6(A)-6(C) , using a template.
[0022] FIG. 9 depicts a second representative embodiment of a swing hammer made in accordance with the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0023] Reference is now made to the figures and accompanying detailed description which have been provided to illustrate exemplary embodiments of the present invention, but are not intended to limit the scope of embodiments of the present invention. Although a particular type of particulate size reduction system is shown in the figures and discussed herein, it should be readily apparent that a device or system constructed in accordance with the present invention can be employed in a variety of other systems, or other applications that do not involve coal as the raw material. In other words, the specific particulate size reduction processes illustrated herein are not vital to gaining the benefits associated with using a system constructed in accordance with the present invention.
[0024] FIGS. 1 and 2 illustrate the general location of a presently preferred embodiment of a swing hammer constructed in accordance with the present invention and employed in an exemplary rotary coal pulverizer 12 , from the exterior of pulverizer 12 . Pulverizer 12 is known as a horizontal type high speed coal mill and is closely based on a duplex model ATRITA® pulverizer sold commercially by Babcock Power Inc. However, this should not be interpreted as limiting the present invention in any way, as many types of pulverizing devices employ similar elements and are suitable for use with the present invention.
[0025] The duplex model is essentially two single models side by side. It should be readily apparent that a swing hammer constructed in accordance with the present invention may also be disposed in a single model. For purposes of ease and convenience in describing the features of the present invention, only a single side of the duplex model is discussed herein.
[0026] As can be seen in FIG. 3 , pulverizer 12 includes a crusher-dryer section 14 , a grinding section 16 and a fan section 18 . A center shaft 20 extends through the pulverizer 12 and defines an axis of rotation. Thus, terms used herein, such as “radially outer” and “radially inner,” therefore refer to the relative distance in a perpendicular direction from the axis defined by center shaft 20 , while “axially inner” and “axially outer” refer to the distance along or parallel to the axis defined by center shaft 20 , wherein the “axially innermost” section in pulverizer 12 is crusher-dryer section 14 .
[0027] Raw coal and primary air enter the crusher-dryer section 14 . Prior art swing hammers 22 mounted on and driven by center shaft 20 , along with impact liners (not shown), operate to crush the coal against a breaker plate, a crusher block and an array of grids (not shown). High temperature primary air is used to flash dry a good deal of the surface moisture of the coal, which helps prepare the coal for combustion. As the high-temperature primary air evaporates moisture from the coal, the temperature of the coal-air mixture is reduced, which significantly reduces the risk of fires within the pulverizer.
[0028] When coal passes through the grid of the crusher-dryer section 14 , it enters the axially outer adjacent grinding section 16 . The major grinding components in grinding section 16 include stationary pegs 24 and clips 26 disposed on a rotating disc or wheel assembly 28 .
[0029] FIGS. 4(A)-4(B) illustrate a plurality of prior art hammers 422 . FIG. 4(A) illustrates a plurality of prior art swing hammers 422 positioned on a wheel 490 . Wheel 490 is adapted and configured to be mounted on a center shaft of a coal pulverizer, as described herein. Two piece hammer 422 is made from a base portion 430 (such as a forging), a pad 440 , and a guard 450 . FIG. 4(B) illustrates a close up view of the hardened pad 440 mounted on the base portion 430 , including mounting holes 470 defined in base portion 430 . The base portion 430 is preferably made from a ductile material to absorb impact when crushing coal. The hardened pad 440 resists wear during the crushing process. The hammer guard 450 protects the softer, inboard portion 435 of base portion 430 and the bonding joint 460 that joins the pad 440 to the base portion 430 . Base portion 430 and guard 450 are rotatably mounted to wheel 490 by way of a pin or bolt 472 . A significant disadvantage of this design is that it is necessary to stock two parts - the combined base portion 430 and wear pad 440 , as well as the guard 450 .
[0030] FIG. 5 illustrates a second, prior art one-piece hammer 522 having a face 530 for impacting coal or other material mounted on a wheel 590 inside of a coal pulverizer. Hammer 522 is rotatably mounted to wheel 590 to pivot about an axis X. Hammer 522 is generally made as a one piece casting from a material such as Manganese steel (approximately 240 BHN) or stainless steel. A hardness rating for the cast stainless steel is not presently available.
[0031] While the prior art hammer depicted in FIG. 5 does exhibit significant resistance to wear, the two piece hammer of FIG. 4 has been found to have at least twice the wear life of the one piece hammer depicted in FIG. 5 . This is possible due to the increased wear resistance.
[0032] In accordance with the invention, swing hammers are provided herein that address problems in the prior art swing hammers described above.
[0033] For purposes of illustration and not limitation, as embodied herein and as depicted in FIGS. 6(A)-6(C) , a first representative embodiment of a swing hammer 622 made in accordance with the invention is depicted. FIG. 6(A) depicts a perspective view of hammer 622 . FIGS. 6(B) and 6(C) depict front and side plan views of hammer 622 , respectively. Swing hammer 622 includes a first end 631 having a mounting portion 633 , a second end 639 , an inboard portion 635 and an outboard portion 637 . As depicted, hammer 622 includes a wear pad 640 attached to a base portion 630 at joint 660 . Wear pad 640 may be attached to base portion 630 in a variety of ways, such as soldering, brazing and the like. In accordance with a preferred embodiment, wear pad 640 is attached to base portion 630 by way of a silver solder material. As with the previously presented swing hammers 422 , 522 , hammer 622 includes a mounting portion including a mounting hole 670 . Base portion 630 and pad 640 are normally formed as a ductile forging and casting, respectively.
[0034] As can be seen, the wear pad 640 is significantly longer than the wear pad 440 depicted in the prior art swing hammer 422 of FIG. 4 , and extends toward mounting hole 670 , over inboard portion 635 of swing hammer 622 . Wear pad 640 has accordingly been shown to help protect the inboard portion 635 of swing hammer, thereby eliminating the need for a separate guard (e.g., 450 ) as in the embodiment 422 depicted in FIGS. 4(A)-4(B) . By providing a one-piece swing hammer 622 and forming the pad material in a more wear resistant material it is possible to have a one piece swing hammer construction that is easier to install, and that is more durable than swing hammers of the prior art.
[0035] FIGS. 7 and 8 depict the results of wear tests of the prior art hammer 422 with guard 450 ( FIG. 7 ) as compared to a hammer 622 made in accordance with the invention ( FIG. 8 ). In each case, the hammers 422 , 622 were operated in a coal pulverizer through six months of typical operation. As depicted in FIG. 7 , a measuring fixture 700 having a profile 710 corresponding to an unused hammer 422 reveals significant wear of the wear pad.
[0036] Significantly, the length of the swing hammer was actually reduced by three-sixteenths of an inch. This is very problematic, as reduction of the length of a swing hammer significantly reduces the effectiveness of the coal pulverizer. For the particular hammer 422 depicted in FIG. 7 , pad 440 is made from an abrasion resistant cast iron material having a Brinnell hardness (“BHN”) of about 600-650. Base portion 430 is made from steel, having a BHN of about 200-255.
[0037] In contrast, as depicted in FIG. 8 , significantly less wear is shown on swing hammer 622 , when comparing swing hammer with its originally installed profile 810 defined by measuring fixture 800 . Most importantly, the length of swing hammer 622 did not change during use, thereby not leading to a decrease in the efficacy of the coal pulverizer. For the particular hammer 622 depicted in FIG. 8 , pad 640 is made from an abrasion resistant cast iron material having a Brinnell hardness (“BHN”) of about 700-750. Base portion 430 is made from steel, having a BHN of about 200-255, as with the embodiment of FIG. 7 .
[0038] As will be appreciated by those of skill in the art, the diverging results depicted in FIGS. 7-8 are actually quite dramatic.
[0039] For purposes of further illustration and not limitation, a second embodiment of a swing hammer 922 made in accordance with the invention is depicted in FIG. 9 . Swing hammer 922 includes a first end 931 having a mounting portion 933 , a second end 939 , an inboard portion 935 and an outboard portion 937 . Swing hammer 922 includes a base portion 930 which may be forged, and a wear pad 940 . A significant difference between the embodiment of FIG. 9 and that of FIG. 6 is that pad 940 includes an interrupted surface defined by a plurality of raised surfaces 942 , 944 . As depicted, a first set of elongated raised surfaces 942 are provided that are oriented at an angle α with respect to a longitudinal axis L of hammer 922 . Similarly, a second set of elongated raised surfaces 944 are oriented at an angle β with respect to axis L. As depicted, the elongated raised surfaces are further oriented at a third angle γ with respect to each other. It will be appreciated that surfaces 942 , 944 can be oriented at any angle with respect to each other and the pad 940 .
[0040] The embodiment of FIG. 9 may be made from a variety of materials, as described herein. For example, the particular hammer 922 depicted in FIG. 9 includes a forged base portion 930 made from steel, similar to the embodiments of FIGS. 4 and 6 . The wear pad 940 may be made from a harder material, such as wear resistant cast iron. Wear pad 940 may be attached to base portion 930 in any suitable manner, such as brazing and the like. The description of materials of construction herein is considered to merely be exemplary and illustrative, and not limiting. For example, if desired, the hammers 622 and 922 depicted herein may be formed from a single material in a single forging operation. However, a two piece construction is preferred to permit portion 939 to be made from a softer, resilient material and the pad made from a high wear resistant material. Moreover, it will be appreciated that the different portions of swing hammers depicted herein may be made from a variety of techniques, such as casting, forging (e.g., ductile forging), and the like.
[0041] It will be appreciated that a variety of materials can be used to make the wear pad portion of swing hammers made in accordance with the invention. Suitable materials may include, for purposes of illustration only, ASTM A532 Class I, Type A Abrasion Resistant Cast Iron, 500 BHN minimum with 1.4-4% Cr and/or ASTM A532, Class II, Type B Abrasion Resistant Cast Iron, 550-600 BHN, with 14-18% Cr, among others. The base portions of hammers made in accordance with the invention may also be made from a variety of materials. Such materials may include, for example, ASTM A128 Grade A, Cast Manganese Steel, 240 BHN maximum, minimum 11% Mn and/or ASTM A743 Grades CF-8, CF-20, Cast Stainless Steel, 18-21% Cr, 8% Ni, among others.
[0042] Without wishing to be limited to a particular theory, it is presently believed that the texturing on the hammer pad of FIG. 9 reduces wear by deflecting coal particles off of the hammer pad surface and exposing less pad surface area to be impacted by coal particles. As such, it is believed that the textured pad 940 helps to reduce wear on the pad surface. As will be appreciated, the depiction of raised surfaces 942 , 944 is merely exemplary. Raised surfaces of any suitable shape may be used, such as round, triangular, rectangular and the like. Similarly, such raised surfaces may be arranged into any suitable pattern or may be arranged randomly. Similarly, an interrupted surface may be formed by forming a plurality of depressions of various shapes in pad 940 instead of or in addition to raised surfaces, as desired.
[0043] Although exemplary and preferred aspects and embodiments of the present invention have been described with a full set of features, it is to be understood that the disclosed system and method may be practiced successfully without the incorporation of each of those features. For example, many industries include applications that utilize raw materials that are first broken up into relatively small sized particles. Accordingly, the raw materials are fed into devices that employ one or more physical processes to reduce the size of the raw material prior to their use. A swing hammer constructed according to the present invention can be utilized for such purposes. Thus, it is to be further understood that modifications and variations may be utilized without departure from the spirit and scope of this inventive system and method, as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the appended claims and their equivalents.
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The invention provides a particulate size reduction system including a grinding chamber, a center shaft defining an axis of rotation and configured for rotational motion within the grinding chamber, a wheel assembly mounted on the center shaft and at least one swing hammer mounted on the wheel assembly. The at least one swing hammer preferably includes a base portion having a first end having a mounting portion for attachment to a wheel assembly of a material treatment system, a second end, an inboard portion proximate the mounting and an outboard portion proximate the second end. The swing hammer also preferably includes a wear pad disposed on the base portion. The wear pad preferably substantially covers a face of the base portion. The wear pad preferably extends from a point proximate the second end of the base portion toward the first end of the base portion to a location proximate the mount.
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FIELD OF THE INVENTION
The present invention is directed to devices for changing the direction of conveying or transport devices. The device includes an upper element and a lower element. The two elements are connected and are relatively movable.
BACKGROUND OF THE INVENTION
Turntables are known from DE 39 10 444 C2. These turntables can be rotated by 180° for coordinating the roll-off or discharge direction of horizontally stored supply rolls.
Rotatable turntables are also known from WO 98/12133 A1. These turntables have guides crossing each other and are provided with sets of track for receiving supply roll conveying carts. These turntables are rotatable over at least 90° and up to preferably 360°, so that the supply roll conveying carts can be shifted between crossing sets of track.
DE 41 19 407 A1 discloses turntables which are driven by the use of a belt via an interspersed friction clutch.
DE 40 06 486 A1 shows a turntable for moving gears, which turntable is driven by a drive motor, that is positively connected to the turntable by a toothed belt.
DE 43 45 090 A1 describes a turntable which is frictionally driven by the use of a cable.
DE 197 08 389 A1 describes a rail switch for a rail-operated floor conveying system. A pivotable support for a rail is frictionally connected with a belt.
A device for direction changing of rail-guided conveying carts is known from U.S. Pat. No. 1,800,722. A pivotable element can be uncoupled from a drive mechanism by the use of a coupling device.
SUMMARY OF THE INVENTION
The object of the present invention is directed to providing devices for changing the direction of conveying devices.
In accordance with the present invention, the object is achieved by the use of a direction changing device which includes an upper element, that receives the material being conveyed, and a lower element. The upper element is supported by the lower element and can be swiveled with respect to it by a drive assembly. The drive assembly is connected to the upper element by a drive belt. A frictional connection exists between one of the drive assembly and the belt or the belt and the upper element.
The advantages which can be achieved by the present invention reside, in particular, in that an effective overload protection is achieved by the frictional force transfer from drive belt or belts to the horizontally swivelable upper element of the device. Since drive forces can be transferred only by friction between the drive belt and the upper element and only up to a defined maximum value, this maximum value will not be exceeded. This means that if forces greater than this defined maximum value act between the drive belt and the upper element, the upper element will slip with respect to the drive belt. Any damage to other components, for example to the motor or to certain gear elements, is thus impossible. An adjustable tensioning roller, which can be brought into contact with the drive belt in various positions, can be employed for setting the forces which can be maximally transferred between the drive belt and the upper element. The tension of the drive belt can be changed by changing the position of the tensioning roller. Correspondingly higher or lower values of the forces transferred by the frictional connection result from changing of the tension of the drive belt by use of the adjustable tensioning roller.
A further advantage of the present invention rests, in particular, in that the force transfer between the drive mechanism and the upper element can be selectively interrupted by the inclusion of a coupling device. The drive mechanism and the upper element are kinematically coupled with each other in a first operational state of the coupling device, so that every positional change of the drive mechanism causes a positional change of the upper element, and each positional change of the upper element causes a positional change of the drive mechanism. In a second operational state of the coupling device, the upper element and the drive mechanism are kinematically decoupled from each other, so that the drive mechanism and the upper element can be moved independently of each other. By use of this coupling, it is made possible, in particular when the drive mechanism fails, to decouple the upper element from the drive mechanism by activating the coupling device, so that the upper element can be manually horizontally swiveled by the operator.
So that a decoupling of the drive mechanism from the upper element can be performed as quickly as possible in connection with devices arranged under the floor, it is preferable to be able to operate the coupling device from the top of the device.
So that the coupling device can be manually decoupled, in particular in case of an electrical failure, it should preferably also be at least manually operable.
An adjustable tensioning roller, in particular, can be employed as a coupling device, which adjustable tensioning roller can be brought into contact with the drive belt in at least two positions. In the first position, the tensioning roller tensions the drive belt at least sufficiently strongly so that a driving force can be frictionally transferred from the drive belt to the upper element. In the second position of the tensioning roller, the belt is relaxed at least sufficiently for the upper element to be rotated with respect to the lower element substantially without having to overcome frictional forces acting between the drive belt and the upper element. The drive mechanism can be coupled in or out by displacing the tensioning roller between its first and second positions.
BRIEF DESCRIPTION OF THE INVENTION
A preferred embodiment of the present invention is represented in the drawings and will be described in greater detail in what follows.
Shown are in:
FIG. 1 , a schematic top plan view of a device for changing the direction of a transport device in accordance with the present invention,
FIG. 2 , a belt drive portion of the device shown in FIG. 1 , also in a top plan view, and in
FIG. 3 , the belt drive shown in FIG. 2 in a cross-sectional view along the section line III—III of FIG. 2 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring initially to FIG. 1 , there may be seen a device 01 for changing the direction of travel of a conveying device or of a transport device, for example the travel direction of rail-guided conveying carts 02 , on which horizontally placed supply rolls of paper or the like can be placed and thus conveyed. The direction changing device 01 is arranged in a recess 32 of a base body 31 , as shown in FIGS. 1 and 3 , in a crossing area between first and second crossing sets of tracks 03 and 04 . The conveying carts 02 , on each of which a horizontally placed supply roll can be conveyed, can be displaced in the longitudinal direction on the sets of tracks 03 and 04 , as indicated by the directional arrow 06 in FIG. 1 .
A rotatably supported upper element 07 of the direction changing device 01 , on which a section of track 08 for receiving the conveying carts 02 is provided, can be horizontally swiveled, in the direction shown by the directional arrow 09 , until the track section 08 is aligned with either of the sets of tracks 03 or 04 . Then the conveying cart 02 is displaced until is completely arranged on the upper element 07 of the direction changing device 01 . Thereafter, the upper element 07 can be swiveled by 90° or, if required for aligning the supply rolls in a different defined longitudinal direction, by 180° or 270°. By this positional change, the track section 08 is aligned with a selected one of the sets of tracks 03 or 04 , and can be further conveyed in the direction of the set of tracks 03 or 04 .
A drive motor 12 , as shown in FIG. 1 , can be employed for driving the upper element 07 , which upper element 07 is seated, rotatable around a central axis 11 , on a lower element, which is not specifically represented in FIG. 1 , which lower element is fixedly connected with the base body 31 . A gear 13 and a driving pinion gear 14 are provided on the power take-off side of the drive motor 12 , which drive motor 12 may be, for example an electric motor 12 . A driving disk 16 is fastened on the underside of the upper element 07 and is opposite the driving pinion gear 14 , as seen in FIG. 2. A belt 17 , for example a toothed belt 17 , is brought into positive engagement with the driving pinion gear 14 for transferring the torque provided by the drive motor 12 on the power take-off side. The belt 17 itself is carried on a smooth-faced circumferential surface 22 of the driving disk 16 and transfers the drive output from the driving pinion gear 14 to the driving disk 16 in a non-positive way by the frictional forces acting between the circumferential surface 22 of the driving disk 16 and the belt 17 .
For setting the tension of the belt 17 , with which tension the belt 17 is stretched over the driving pinion gear 14 and over the circumferential surface 22 of the driving disk 16 , it is possible to push a pivotably seated tensioning roller assembly, generally at 18 , against the belt 17 . Pivotable tensioning roller assembly 18 is depicted generally in FIG. 1 .
The main components of the belt drive of the direction changing device 01 can be seen in the top a view shown in FIG. 2 . The inner surface of the drive belt 17 comes into positive contact with the circumferential surface 22 of the driving pinion gear 14 , so that it is possible by the provision of a rotatory drive of the driving pinion gear 14 , in accordance with the directional arrow 19 , to cause a forwardly or rearwardly directed control movement of the belt 17 , which belt movement direction is indicated by the directional arrow 21 . The inner surface of the belt 17 itself rests against the smooth-faced outer circumferential surface 22 of the driving disk 16 . The driving disk 16 is thus frictionally driven by its contact with the inside of the belt 17 , so that, as a result, a swiveling or rotational movement of the driving disk 16 and of the upper element 07 , which is arranged above the driving disk 16 , in accordance with a directional arrow 23 , again as seen in FIG. 2 , can be provided. The drive arrangement 12 , 13 , 14 can alternatively be frictionally connected and the driving disk 16 can be positively connected with the belt 17 .
The belt 17 is deflected by a deflection roller 24 and by a tensioning roller 26 , which rollers 24 and 26 are situated between the driving pinion gear 14 and the driving disk 16 , as shown most clearly in FIG. 2 . The tensioning roller 26 is rotatably supported on a first or outboard end 37 of a pivot arm 27 . The pivot arm 27 can be pivoted at its second or inner end 38 around a pivot shaft 29 in accordance with a directional arrow 28 . Depending on the engagement position of the pivot arm 27 , the tensioning roller 26 , which is part of the tensioning roller assembly 18 , is pressed against the belt 17 with a higher or lower pressure, so that the tension of the belt 17 can be changed by use of this tensioning roller.
The frictional forces which can be transferred from the belt 17 to the driving disk 16 are directly correlated with the tension of the belt 17 , which belt tension can be affected by the tensioning roller 26 . It follows from this that, with an appropriate relaxation of the belt 17 , by swiveling the tensioning roller 26 outward, the drive output which can be maximally transferred between the belt 17 and the driving disk 16 can be changed. As soon as the belt 17 is relaxed to the extent that it essentially rests without contact pressure on the smooth, outer circumferential surface 22 of the driving disk 16 , no drive output can be transferred from the driving pinion gear 14 to the driving disk 16 .
As a result, it is therefore possible to use the tensioning roller 26 in the manner of a coupling device by pivoting the pivot arm 27 . By using the tensioning roller 26 to exert an appropriate tension on the belt 17 , the belt 17 will now be forced against the circumferential outer surface 22 of the driving disk 16 with such a high contact pressure that the upper element 07 can only be swiveled while the driving pinion gear 14 is simultaneously rotating. If the tensioning roller 26 is displaced by pivoting the pivot arm 27 , so that the belt 17 is essentially no longer under tension, the driving disk 16 can slide with respect to the belt 17 essentially without resistance, so that, for example, the upper element 07 can be manually swiveled without the driving pinion gear 14 or the drive belt 17 having to rotate together with the upper element 07 .
The mechanism which is operable for the adjustment of the tension roller 26 is represented in FIG. 3 . So that the direction changing device 01 can be arranged under the floor, a recess 32 , for example a bed, which is only partially shown in FIG. 3 , is provided in the base body 31 . The direction changing device 01 can be arranged in recess 32 in such a way that the top of the upper element 07 essentially extends in the horizontal plane 33 that is defined by the top of the base body 31 . In the preferred embodiment of the present invention, the drive mechanism of the direction changing device 01 , which essentially consists of the drive motor 12 , the gear 13 and the driving pinion gear 17 , is also arranged in the recess 32 , wherein the drive motor 12 is fastened to the bottom 34 of the recess 32 . The bottom 34 of the recess 32 forms the lower, fixed element of the device 01 for changing a direction of travel of a conveying device.
The tensioning roller 26 is rotatably seated, by the use of a rolling bearing 35 on a bolt 36 . The bolt 36 itself has been screwed into the pivot arm 27 on the first or outboard end 37 of the pivot arm 27 . The second or inner end 38 of the pivot arm 27 has a cutout or aperture, in which a sleeve 39 , for example embodied as an elongated tube, can be fastened. A shaft 41 extends along the length of the interior of the sleeve 39 . A lower end 42 of the shaft 41 has been glued, by the use of an adhesive, into a cutout of the base body 31 and is used as an anchoring element. A tensioning element 44 which, in the preferred embodiment, is provided in the manner of a tensioning screw 44 , can be actuated by screwing the tensioning screw 44 in. Starting at a defined screw insertion depth, the tensioning element 44 engages indirectly through an intermediate washer 46 , the upper end 47 of the elongated sleeve 39 . By further screwing in of the tensioning element 44 , the distance between the bottom 34 of the recess 32 and the underside of the washer 46 is further shortened, so that, as a result, the elongated sleeve 39 can be clamped between the washer 46 and the base body 31 by screwing in the tensioning element 44 . So that the tensioning force exerted through the increasing screwing in of the tensioning element 44 rises as continuously and as linearly as possible, and not suddenly, an elastic element 48 , for example a rubber washer 48 , is positioned between the lower end 45 of the sleeve 39 and the bottom 34 of the recess 32 , which rubber washer 48 is elastically compressed when the sleeve 39 is clamped down by screwing in of the tensioning element or screw or bolt 44 .
To change the tension imparted to the belt 17 by the tensioning roller 26 , the tensioning element 44 is released or screwed out sufficiently far, so that the elongated sleeve 39 can be turned on the shaft 41 . Because of this, the position of the tensioning roller 26 relative to the belt 17 changes, so that a desired belt tension can be set. For actuating the coupling device, which is substantially constituted by the tensioning roller 26 , the pivot arm 27 , the sleeve 39 and the shaft 41 , simply and essentially without having to disassemble other components, a cutout 49 is provided above the tensioning element 44 in a cover plate 51 , by use of which cover plate 51 the recess 32 can be covered. A tool, for example a socket wrench, can be passed through the cutout 49 and the tensioning element 44 can be actuated in this manner.
For setting the tension of the belt 17 it is advantageous that the tensioning element 44 does not need to be completely released for resetting the pivot arm 27 . Otherwise it would be necessary, during the adjustment of the pivot arm 27 , to simultaneously hold the sleeve 39 in place and to tighten the tensioning element 44 . For this reason, surfaces 53 , on which tools can act, are provided at the upper end 47 of the elongated sleeve 39 , for example in the shape of a hexagon 53 , with which hexagonal surfaces 53 a tool for rotating the sleeve 39 can be brought into engagement. In that case, to adjust the pivot arm 27 , the tensioning element 44 is only sufficiently loosened or screwed out so that the sleeve 39 can be rotated with the aid of a tool, for example a tool in the form of a hexagon sprocket. Following the adjustment of the pivot arm 27 , the tensioning element 44 is again sufficiently tightened so that the sleeve 39 is clamped with a sufficient holding force. Thereafter, the cutout 49 in the cover plate 51 can be closed by the use of an appropriately shaped cover element 52 .
As a result, the coupling device constituted by the tensioning roller 26 , the pivot arm 27 , the elongated sleeve 39 and the shaft 41 can therefore be manually actuated by loosening, or screwing in of the tensioning element 44 and by subsequent rotation of the sleeve 39 . It is thus assured that the drive mechanism, constituted by the drive motor 12 , the gear 13 and the driving pinion gear 14 , can be decoupled at any time, in particular in case of a possible failure of the drive mechanism, from the upper element 07 of the device 01 , so that the upper element 07 can be manually swiveled by the operators.
Since the sleeve 39 and the shaft 41 extend upward to a location close to the underside of the cover plate 51 , it is possible to operate the coupling device without having to disassemble other components, except for the removal of the cover plate 52 .
The conveying cart 02 is primarily configured as a rail-guided conveying cart 02 for receiving paper rolls for conveyance to a roll changer of a rotary printing press.
While a preferred embodiment of a device for changing a direction of travel of a conveying or a transport device, in accordance with the present invention has been set forth fully and completely hereinabove, it will be apparent to one of skill in the art that a number of changes in, for example the sizes of the conveying carts, the type of rotary printing press used with the device, and the like could be made without departing from the true spirit and scope of the present invention which is accordingly to be limited only by the following claims.
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A device that is usable to change the direction of a transport assembly, on which feed roller may be transported, includes a lower section and an upper section. The upper section is pivotally mounted on the lower section. The transport assembly is arranged on the side or on the top of the upper section and the upper section can be pivoted by an angular amount, relative to the lower section, by use of a drive unit. A drive motor of the drive unit has its output transmitted to the upper section by a drive belt. A positive drive exists between the motor and belt and a friction drive exists between the belt and the upper section.
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BACKGROUND
[0001] 1. Technical Field
[0002] The present invention relates to double fabric blinds and, more particularly, to a device for adjusting a fabric angle of double fabric blinds.
[0003] 2. Background Art
[0004] Referring to FIGS. 1 and 2 , double fabric blinds generally use a double fabric, in which a front sheet 1 and a rear sheet 2 woven from mesh are coupled to a plurality of connection fabrics 3 extending between the front sheet 1 and the rear sheet 2 , as a fabric for blinds 4 wound around a winding rod 6 . Each of the connection fabrics 3 has a substantially S-shaped section and is connected in the longitudinal direction such that the front sheet 1 is spaced at a predetermined distance apart from the rear sheet 2 . The front and rear sheets 1 and 2 are formed from a transparent material woven from mesh, and the plurality of connection fabrics 3 are formed from a translucent material which is more flexible than those of the front and rear sheets 1 and 2 . The fabric 4 for the double fabric blinds allows light from the outside to be transmitted therein via the front and rear sheets 1 and 2 when the connection fabrics 3 are spread.
[0005] As illustrated in FIG. 2 , when one of the front and rear sheets 1 and 2 moves upward, the various connection fabrics 3 are folded, and thus the front sheet 1 and the rear sheet 2 are almost in contact with each other. Simultaneously, since the plurality of connection fabrics 3 are in contact with each other, the blinds enter a translucent state in which light is transmitted through the front and rear sheets 1 and 2 , but is at least partially obscured.
[0006] Turning to FIG. 3 , roll blinds 9 have been manufactured by using the fabric 4 of the double fabric blinds. Roll blinds 9 can include an upper case 6 , which is coupled to the winding rod 5 for winding the fabric 4 of the double fabric blinds, and a lower end bar 7 having a weight on the lower end of the double fabric. Also, a driving roller 8 is disposed on one end of the winding rod 5 so as to move the double fabric in the vertical direction, and an adjustable string 8 a for rotating the driving roller 8 is provided. In this state, when the adjustable string 8 a is pulled, the double fabric for blinds 4 moves downward while the driving roller 8 is rotated. The connection fabric 3 disposed between the front sheet 1 and the rear sheet 2 moves downward in the folded state, and when the fabric for blinds 4 moves down to the bottom, the folded connection fabrics 3 are spread due to the weight of the lower end bar 7 .
[0007] Since conventional roll blinds have a structure in which a plurality of vanes are spread due to the weight of the lower end bar only when the double fabric moves down to the bottom, there is a limitation in that the roll blinds include no elements for allowing a user to spread the folded connection fabric at a desired position, particularly at the middle or upper positions of the double fabric, and/or adjust a spread angle of the connection fabric. Also, the conventional design includes a drop-down string (adjustable string 8 a ) which poses a safety hazard for children who may become entangled in the string.
[0008] To solve the abovementioned limitation, “blinds with adjustment for the angle of a double fabric” are disclosed in Korean patent gazette No. 10-943408, a previously owned patent also owned by the present applicant. Since the double blinds of the previously registered patent include a driving body, an angle adjustment component, two rollers, and two adjustable strings, the structure of the blinds in this configuration is relatively complicated. Although a degree of openness of the front sheet of the double fabric is adjustable via a friction member of the angle adjustment component, the abrasiveness (and associated coefficient of friction) of the friction member may deteriorate after being used for a long time, reducing the degree of openness to which the double fabric can be adjusted.
BRIEF SUMMARY
[0009] One Aspect of the present invention provides adjusting of double fabric blinds and, more particularly, a device for adjusting the fabric angle of the double fabric blinds, which is capable of finely adjusting a degree of openness of such a fabric since a plurality (e.g., four or eight) of balls are sequentially held and inserted in a holding groove of a rotation component, and are rotated in a guide groove of a stopper at 90 degrees or 45 degrees, thereby reducing accidents since an adjustable string is not used. Also, the device can be easily operated since a separate lower end bar is formed on the lower ends of the front sheet and rear sheet, which can provide the same function as a handle.
[0010] To achieve the abovementioned functions, embodiments of the present invention provide a device for adjusting the fabric angle of double fabric blinds, comprising: a cover provided with an insertion hole having a hook protrusion formed therein, wherein coupling protrusions are disposed symmetrical to each other on the inner circumferential surface of the cover and protrude outward; a rotation component having coupling grooves which are coupled to the coupling protrusions of the cover, disposed symmetrical to each other on the outer circumferential surface of the rotation component, and recessed inward, and insertion grooves and a coupling hole formed in the inner circumferential surface of said rotation component, wherein a plurality of balls are inserted into the insertion grooves and a stopper is coupled to the coupling hole; a stopper having a shaft insertion hole which passes through same and has a coupling groove coupled to the hook protrusion of a spring at the lower end of said stopper, so as to be inserted into the coupling hole of the rotation component, and guide grooves, inclined grooves, and holding grooves in the outer circumferential surface of same, wherein the guide grooves and inclined grooves allow the balls to be rotated, and the holding grooves hold the balls; a fixing shaft, the front of which has the coupling protrusion coupled to a washer and the rear of which has the spring coupled to the hook protrusion projecting outward, inserted into the shaft insertion hole of the stopper; and blinds which have the plurality of balls inserted into the insertion grooves of the rotation component, to adjust the angle of the double fabric by moving in the guide groove and coupling the stopper to the rotation component. The device is characterized in that when the rotation component is rotated after four balls are inserted into the guide groove of the stopper and the rotation component is coupled to the stopper, a degree of openness of the double fabric is adjusted while the four balls are sequentially held by the holding groove as the rotation component is rotated at 90 degrees.
[0011] The present invention can provide the following technical effects.
[0012] First, a user may easily and simply adjust the degree of openness of the double fabric as desired.
[0013] Second, the opened angle of the double fabric may be finely adjusted by controlling the number of the balls inserted into the insertion grooves of the rotation component.
[0014] Third, the device of the present invention is effective in that a ball chain or an adjustable string is not used, thereby improving safety for the user.
[0015] Fourth, the device has a simple structure and reduces malfunctions from occurring during operation, thereby also reducing manufacturing costs.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIGS. 1-3 are views illustrating a configuration and operation of conventional double fabric blinds.
[0017] FIG. 4 is a cross-sectional view illustrating double blinds of applicant's previously registered patent disclosed in Korean patent gazette No. 10-943408.
[0018] FIG. 5 is a perspective exploded view illustrating the configuration of a device for adjusting a fabric angle of double fabric blinds according to embodiments of the present invention.
[0019] FIG. 6 is a cross-sectional view illustrating a configuration of the device for adjusting the fabric angle of double fabric blinds according to embodiments of the present invention.
[0020] FIG. 7 is a perspective view illustrating a state in which a rotation component is coupled to a cover of the device for adjusting the fabric angle of double fabric blinds according to embodiments of the present invention.
[0021] FIG. 8 is a perspective view illustrating a state in which all elements of the device for adjusting the fabric angle of double fabric blinds according to embodiments of the present invention are coupled to each other.
[0022] FIGS. 9-15 are views illustrating a state in which the device for adjusting the fabric angle of double fabric blinds according to embodiments of the present invention is used.
DETAILED DESCRIPTION
[0023] Hereinafter, the preferred embodiments of the present invention will be described below in more detail with reference to the accompanying drawings.
[0024] Reference number 300 represents a body of a device for adjusting a fabric angle of double fabric blinds according to embodiments of the present invention. The body 300 includes: a cover 310 having a hook protrusion 312 on which a coupling protrusion 311 is formed; a rotation component 320 having an outer circumferential surface on which coupling grooves 321 disposed symmetrically relative to each other are formed, and an inner circumferential surface in which an insertion groove 322 and a coupling hole 323 are formed; a stopper 330 having a shaft insertion hole 332 and a coupling groove 331 formed on one surface of the outer circumferential surface of the stopper 330 ; the stopper having a guide groove 333 , an inclined groove 334 , and a holding groove 335 formed on the outer circumferential surface thereof, wherein a ball 350 is rotated in the guide grooves and inclined grooves 333 and 334 and held in the holding groove 335 ; and a fixing shaft 340 , the front of which has a coupling protrusion 342 coupled to which a washer 341 and the rear of which is coupled to a spring 343 having a hook protrusion 343 protruding outward.
[0025] The cover 310 has an insertion hole and a hook protrusion in which coupling protrusions are formed symmetrical to each other on the inner circumferential surface of the cover, protruding outward. Also, a plurality of protrusions 314 coupled to a winding drum around which the double fabric is wound are formed on the outer circumferential surface of the cover 310 . Any desired number of protrusions 314 can be provided on cover 310 . The coupling grooves 321 , which are symmetrical to each other and can be in the form of semicircular grooves, are formed in the outer circumferential surface of the rotation component 320 . The coupling hole 323 having the insertion grooves 322 , where a plurality of balls 350 are inserted, can be formed in the inner circumferential surface of the rotation component.
[0026] The insertion groove 323 can have a semicircular shape and extend in a longitudinal direction within the rotation component 320 , which is illustrated in FIG. 6 . Also, the plurality of balls 350 can be inserted into the insertion groove 323 and used as discussed herein. In particular, four balls 350 can be inserted into the insertion groove, or eight balls 350 may alternatively be inserted for use. In other embodiments, more than eight balls 350 may be used if desired. The fixing shaft 340 is inserted into the coupling hole 323 of the rotation component 320 . The stopper 330 is a pipe which can have a cylindrical shape. The coupling groove 331 , to which the hook protrusion 343 of the spring 344 is coupled, is formed on one area of the inner circumferential surface of the stopper and has a predetermined length. The shaft insertion hole 332 is formed in the stopper. The guide grooves and inclined grooves 333 and 334 , in which each of the balls 350 is moved, and the holding groove 335 for holding the ball 350 are formed in the outer circumferential surface of the stopper 330 .
[0027] One surface of the ball 350 contacts the guide groove 333 of the stopper 330 , and another surface of the ball contacts the insertion groove 322 of the rotation component 320 . Thus, the rotation component 320 may hold a rotation according to the movement of the ball 350 . The coupling protrusion 342 , to which the washer 341 is coupled, is formed on the front of the fixing shaft 340 , and the spring 344 having the hook protrusion 343 protruding outward is coupled to the rear of the fixing shaft. A coupling groove 345 is formed in the central portion of the rear surface of the shaft 340 so that a coupling protrusion of a bracket is inserted. The hook protrusion 343 of the spring 344 can be disposed on the outer circumferential surface of the fixing shaft 340 and coupled to the coupling groove 331 of the stopper 330 as described above, and thus, the stopper 330 is held by the hook protrusion.
[0028] A method for operating the abovementioned device to adjust the fabric angle of the double fabric blinds according to embodiments of the present invention will be described with reference to FIGS. 9-13 . First, the coupling protrusion of the bracket is coupled to the coupling groove 345 formed in the rear surface of the fixing shaft 340 , and a rotor rotated due to the elastic force of a well-known spring is mounted on a spring on a surface opposite the rear surface of the fixing shaft. Further, the winding drum, around which a double fabric 110 made of a connection fabric 113 connecting a front sheet 111 and a rear sheet 112 is wound, may be coupled and fixed to the protrusion 314 of the cover 310 . Lower end rods 371 and 372 are provided on the lower ends of the front and rear sheets 111 and 112 , respectively. Each of the lower end rods 371 and 372 can have a cylindrical shape and the same length as the width of the fabric. A string provided with a handle may be provided at the lower side of the lower end rod 371 of the front sheet for use.
[0029] As illustrated in FIGS. 9 and 10 , the lower end rod 371 of the front sheet may be gripped and pulled downward in a state in which the double fabric 110 is entirely wound around the winding drum, thereby moving the double fabric in the vertical direction. The four balls 350 located in a front side of the insertion groove 322 of the rotation component 320 are rotated in the guide groove 333 of the stopper 330 . Simultaneously, the double fabric moves downward while the rotor on the opposite side is loading the spring. The fixing shaft 340 is in a fixed state, and the stopper 330 is rotated in a direction opposite to that of the spring 344 wound in a state in which the hook protrusion 343 of the spring 344 is coupled to the stopper. Simultaneously, the double fabric moves downward while the rotation component 320 is engaged with the stopper 340 and the four balls 350 , and the cover 310 inserted into the coupling groove 321 of the rotation component 320 are rotated in the same direction.
[0030] To allow sunlight to be transmitted to the inside by adjusting an degree of openness of the double fabric 110 in a state in which the double fabric 110 has moved downward to the lowest end, when the lower end rod 372 of the rear sheet is gripped and pulled downward as illustrated in FIG. 11 , a first ball 350 of the four balls 350 moves along the inclined groove 334 and is located and stopped in the holding groove 335 as illustrated in FIG. 12 , and simultaneously, the front sheet 111 moves upward to open the double fabric 110 as illustrated in FIG. 13 . In particular, the first ball 350 of the four balls is held in the holding groove 335 when the rotation component 320 is rotated by 90 degrees to adjust the degree of openness of the double fabric, and when the lower end rod 372 of the rear sheet is pulled downward again, a second ball 350 is held in the holding groove 335 when the rotation component 320 is rotated by 90 degrees to further increase the degree of openness of the double fabric.
[0031] As described above, as the rotation component 320 is rotated by 90 degrees, the plurality of balls 350 may be sequentially held in the holding groove 355 to finely adjust the degree of openness of the double fabric. Also, according to embodiments of the present invention, eight balls 350 can be coupled to the insertion grooves 322 of the rotation component 320 , and the stopper 330 is inserted into the rotation component 320 , and thus the balls 350 are located in the guide groove 333 formed in the outer circumferential surface of the stopper 330 . In this state, as illustrated in FIG. 11 , when the lower end rod 372 of the rear sheet is gripped and pulled downward, the first ball 350 of the eight balls is held in the holding groove 335 when the rotation component 320 is rotated by 45 degrees to adjust the degree of openness of the double fabric, and when the lower end rod 372 of the rear sheet is pulled downward again, the second ball 350 is held in the holding groove 335 when the rotation component 320 is rotated by 45 degrees to further open the degree of openness of the double fabric.
[0032] As described above, as the rotation component 320 is rotated by 45 degrees, the eight balls 350 may be sequentially held in the holding groove 355 to finely adjust the degree of openness of the double fabric. In this state, when the lower end rod 372 of the rear sheet is pulled downward such that the roller turns more than a holding angle, the ball 350 is removed from the holding groove 335 as illustrated in FIGS. 14 and 15 . Simultaneously, the rotor on the opposite side is rotated as the spring loses its tension. The cover, to which the winding drum is coupled, is rotated and causes the double fabric 110 to move upward. The ball 350 may be located in the guide groove 333 of the stopper 330 , which is the initial state.
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The present invention relates to double fabric blinds and, more particularly, to a device for adjusting a fabric angle of the double fabric blinds, which is capable of finely adjusting an degree of openness of a front sheet, wherein a plurality of balls are sequentially held in a holding groove, e.g., as four or eight balls, inserted into an insertion groove of a rotation component, wherein the plurality of balls are rotated in a guide groove of a stopper by approximately 90 degrees or 45 degrees, thereby improving safety and omitting the use of a conventional string.
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This is a divisional of U.S. application Ser. No. 10/134,780, filed Apr. 29, 2002, the entire disclosure of which is incorporated herein by reference.
FIELD OF THE INVENTION
The disclosure relates generally to peer-to-peer protocols, and more particularly to security framework infrastructures for peer-to-peer protocols.
BACKGROUND
Peer-to-peer (P2P) communication, and in fact all types of communication, depend on the possibility of establishing valid connections between selected entities. However, entities may have one or several addresses that may vary because the entities move in the network, because the topology changes, or because an address lease cannot be renewed. A classic architectural solution to this addressing problem is thus to assign to each entity a stable name, and to “resolve” this name to a current address when a connection is needed. This name to address translation must be very robust, and it must also allow for easy and fast updates.
To increase the likelihood that an entity's address may be found by those seeking to connect to it, many peer-to-peer protocols, including the Peer Name Resolution Protocol (PNRP), allow entities to publish their address through various mechanisms. Some protocols also allow a client to acquire knowledge of other entities' addresses through the processing of requests from others in the network. Indeed, it is this acquisition of address knowledge that enables successful operation of peer-to-peer networks. That is, the better the information about other peers in the network, the greater the likelihood that a search for a particular resource will converge.
However, without a robust security infrastructure underlying the peer-to-peer protocol, malicious entities can easily disrupt the ability for such peer-to-peer systems to converge. Such disruptions may be caused, for example, by an entity that engages in identity theft. In such an identity theft attack on the peer-to-peer network, a malicious node publishes address information for identifications (IDs) with which it does not have an authorized relationship, i.e. it is neither the owner nor a group member, etc. A malicious entity could also intercept and/or respond first before the good node responds, thus appearing to be the good node.
Commonly, P2P network attacks may attempt to disrupt or exhaust node or network resources. In PNRP, a malicious entity could also obstruct PNRP resolution by flooding the network with bad information so that other entities in the network would tend to forward requests to nonexistent nodes (which would adversely affect the convergence of searches), or to nodes controlled by the attacker. PNRP's name resolution ability could also be degraded by modifying the RESOLVE packet used to discover resources before forwarding it to a next node, or by sending an invalid RESPONSE to back to the requester that generated the RESOLVE packet. A malicious entity could also attempt to disrupt the operation of the peer-to-peer network by trying to ensure that searches will not converge by, for example, instead of forwarding the search to a node in its cache that is closer to the ID to aid in the search convergence, forwarding the search to a node that is further away from the requested ID. Alternatively, the malicious entity could simply not respond to the search request at all. The PNRP resolution could be further hampered by a malicious node sending an invalid BYE message on behalf of a valid ID. As a result, other nodes in the cloud will remove this valid ID from their cache, decreasing the number of valid nodes stored therein.
While simply validating address certificates may prevent the identity theft problem, such is ineffective against an attack that impedes PNRP resolution. An attacker can continue to generate verifiable address certificates (or have them pre-generated) and flood the corresponding IDs in the peer-to-peer cloud. If any of the nodes attempts to verify ownership of the ID, the attacker would be able to verify that it is the owner for the flooded IDs because, in fact, it is. However, if the attacker manages to generate enough IDs it can bring most of the peer-to-peer searches to one of the nodes it controls. Once a malicious node brings the search to controlled node, the attacker fairly controls and directs the operation of the network.
A malicious node may also attempt a denial of service (DoS) attack. When a P2P node changes, it may publish its new information to other network nodes. If all the nodes that learn about the new node records try to perform an ID ownership check, a storm of network activity against the advertised ID owner will occur. Exploiting this weakness, an attacker could mount an internet protocol (IP) DoS attack against a certain target by making that target very popular. For example, if a malicious entity advertises an Internet Website IP address as the updated node's ID IP, all the nodes in the peer-to-peer network that receive this advertised IP will try to connect to that IP to verify the authenticity of the record. Of course, the Website's server will not be able to verify ownership of the ID because the attacker generated this information. However, the damage has already been done. That is, the attacker convinced a good part of the peer-to-peer community to flood the IP address with validation requests and may have effectively shut it down.
Another type of DoS attack that overwhelms a node or a cloud by exhausting one or more resources occurs when a malicious node sends a large volume of invalid/valid peer address certificates (PACs) to a single node (e.g. by using FLOOD/RESOLVE/SOLICIT packets). The node that receives these PACs will consume all its CPU trying to verify all of the PACs. Similarly, by sending invalid FLOOD/RESOLVE packets, a malicious node will achieve packet multiplication within the cloud. That is, the malicious node can consume network bandwidth for a PNRP cloud using a small number of such packets because the node to which these packets are sent will respond by sending additional packets. Network bandwidth multiplication can also be achieved by a malicious node by sending bogus REQUEST messages to which good nodes will respond by FLOODing the PACs, which are of a larger size than the REQUEST.
A malicious node can also perpetrate an attack in the PNRP cloud by obstructing the initial node synch up. That is, to join the PNRP cloud a node tries to connect to one of the nodes already present in the PNRP cloud. If the node tries to connect to the malicious node, it can be completely controlled by that malicious node. Further, a malicious node can send invalid REQUEST packets when two good nodes are involved in the synchronization process. This is a type of DoS attack that will hamper the synch up. Because the invalid REQUEST packets generate FLOOD messages in response, initial node synch up may be hindered.
There exists a need in the art, therefore, for security mechanisms that will ensure the integrity of the P2P cloud by preventing or mitigating the effect of such attacks.
SUMMARY
The concepts disclosed herein involve a new and improved method for inhibiting a malicious node's ability to disrupt normal operation of a peer-to-peer network. Specifically, the disclosure presents methods to address various types of attacks that may be launched by a malicious node, including identity theft attacks, denial of service attacks, attacks that merely attempt to hamper the address resolution in the peer-to-peer network, as well as attacks that attempt to hamper a new node's ability to join and participate in the peer-to-peer network.
The security infrastructure and methods presented allow both secure and insecure identities to be used by nodes by making them self-verifying. When necessary or opportunistic, ID ownership is validated by piggybacking the validation on existing messages or, if necessary, by sending a small inquire message. The probability of connecting initially to a malicious node is reduced by randomly selecting the connection node. Further, information from malicious nodes is identified and can be disregarded by maintaining information about prior communications requiring a future response. Denial of service attacks are inhibited by allowing the node to disregard requests when its resource utilization exceeds a predetermined limit. The ability for a malicious node to remove a valid node is reduced by requiring revocation certificates to be signed by the node to be removed.
In accordance with one embodiment, a method of generating a self-verifiable insecure peer address certificate (PAC) that will prevent a malicious node from publishing another node's secure identification in an insecure PAC in the peer-to-peer network is presented. This method comprises the steps of generating an insecure PAC for a resource discoverable in the peer-to-peer network. The resource has a peer-to-peer identification (ID). The method further includes the step of including a uniform resource identifier (URI) in the insecure PAC from which the peer-to-peer ID is derived. Preferably, the URI is in the format “p2p://URI”. The peer-to-peer ID may also be insecure.
In a further embodiment, a method of opportunistically validating a peer address certificate at a first node in a peer-to-peer network is presented. This first node utilizes a multilevel cache for storage of peer address certificates, and the method comprises the steps of receiving a peer address certificate (PAC) purportedly from a second node and determining the PAC storage level in the multilevel cache. When the PAC is to be stored in one of two lowest cache levels, the method places the PAC in a set aside list, generates an INQUIRE message containing an ID of the PAC to be validated, and transmits the INQUIRE message to the second node. When the PAC is to be stored in an upper cache level other than one of the two lowest cache levels, the method stores the PAC in the upper cache level marked as ‘not validated’. In this case, the PAC will be validated the first time it is used. The method may also request a certificate chain for the PAC.
In one embodiment, creating of the INQUIRE message comprises the step of generating a transaction ID to be included in the INQUIRE message. When an AUTHORITY message is received from the second node in response to the INQUIRE message, the PAC is removed from the set aside list and is stored in one of the two lowest cache levels. If a certificate chain was requested, the AUTHORITY message is examined to determine if the certificate chain is present and valid. If the AUTHORITY is present and valid, the PAC is stored in the one of the two lowest cache levels, and if not, it is deleted. A transaction ID may also be used to ensure that the AUTHORITY message is in response to a prior communication.
In a further embodiment, a method of discovering a node in a peer-to-peer network in a manner that reduces the probability of connecting to a malicious node is presented. This method comprises the steps of broadcasting a discovery message in the peer-to-peer network without including any IDs locally registered, receiving a response from a node in the peer-to-peer network, and establishing a peering relationship with the node. In one embodiment, the step of receiving a response from a node comprises the step of receiving a response from at least two nodes in the peer-to-peer network. In this situation, the step of establishing a peering relationship with the node comprises the steps of randomly selecting one of the at least two nodes and establishing a peering relationship with the randomly selected one of the at least two nodes.
In yet a further embodiment, a method of inhibiting a denial of service attack based on a synchronization process in a peer-to-peer network is presented. This method comprises the steps of receiving a SOLICIT message requesting cache synchronization from a first node containing a peer address certificate (PAC), examining the PAC to determine its validity, and dropping the SOLICIT packet when the step of examining the PAC determines that the PAC is not valid. Preferably, when the step of examining the PAC determines that the PAC is valid, the method further comprises the steps of generating a nonce, encrypting the nonce with a first node public key of the first node, generating an ADVERTISE message including the encrypted nonce, and sending the ADVERTISE message to the first node. When a REQUEST message is received from the first node, the method examines the REQUEST message to determine if the first node was able to decrypt the encrypted nonce, and processes the REQUEST message when the first node was able to decrypt the encrypted nonce.
Preferably, this method further comprises the steps of maintaining connection information specifically identifying the communication with the first node, examining the REQUEST message to ensure that it is specifically related to the ADVERTISE message, and rejecting the REQUEST message when it is not specifically related to the ADVERTISE message. In one embodiment, the step of maintaining connection information specifically identifying the communication with the first node comprises the steps of calculating a first bitpos as the hash of the nonce and the first node's identity, and setting a bit at the first bitpos in a bit vector. When this is done, the step of examining the REQUEST message comprises the steps of extracting the nonce and the first node's identity from the REQUEST message, calculating a second bitpos as the hash of the nonce and the first node's identity, examining the bit vector to determine if it has a bit set corresponding to the second bitpos, and indicating that the REQUEST is not specifically related to the ADVERTISE message when the step of examining the bit vector does not find a bit set corresponding to the second bitpos. Alternatively, the nonce may be used directly as the bitpos. In this case, when the REQUEST is received, the bitpos corresponding to the enclosed nonce is checked. If it is set, this is a valid REQUEST and the bitpos is cleared. Otherwise, this is an invalid REQUEST or replay attack, and the REQUEST is discarded.
In yet a further embodiment, a method of inhibiting a denial of service attack based on a synchronization process in a peer-to-peer network comprises the steps of receiving a REQUEST message purportedly from a first node, determining if the REQUEST message is in response to prior communication with the first node, and rejecting the REQUEST message when the REQUEST message is not in response to prior communication with the first node. Preferably, the step of determining if the REQUEST message is in response to prior communication comprises the steps of extracting a nonce and an identity purportedly of the first node from the REQUEST message, calculating a bitpos as the hash of the nonce and the identity, examining a bit vector to determine if it has a bit set corresponding to the bitpos, and indicating that the REQUEST is not in response to prior communication with the first node when there is no bit set corresponding to the bitpos.
A method of inhibiting denial of service attacks based on node resource consumption in a peer-to-peer network is also presented. This method comprises the steps of receiving a message from a node in the peer-to-peer network, examining current resource utilization, and rejecting processing of the message when the current resource utilization is above a predetermined level. When a RESOLVE message is received, the step of rejecting processing of the message comprises the step of sending an AUTHORITY message to the first node. This AUTHORITY message contains an indication that the RESOLVE message will not be processed because the current resource utilization too high. When a FLOOD message is received containing a peer address certificate (PAC) and the method determines that the PAC should be stored in one of two lowest cache levels, the step of rejecting processing of the message comprises the step of placing the PAC in a set aside list for later processing. If the method determines that the PAC should be stored in a cache level higher than two lowest cache levels, the step of rejecting processing of the message comprises the step of rejecting the FLOOD message.
In another embodiment, a method of inhibiting denial of service attacks based on node bandwidth consumption in a peer-to-peer network is presented. This method comprises the steps of receiving a request for cache synchronization from a node in the peer-to-peer network, examining a metric indicating a number of cache synchronizations performed in the past, and rejecting processing of the request for cache synchronization when the number of cache synchronizations performed in the past exceeds a predetermined maximum. In a further embodiment, the method examines the metric to determine the number of cache synchronizations performed during a predetermined preceding period of time. In this embodiment the step of rejecting processing of the request comprises the step of rejecting processing of the request for cache synchronization when the number of cache synchronizations performed in the preceding period of time exceeds a predetermined maximum.
In another embodiment, a method of inhibiting a search based DoS attack in a peer-to-peer network comprises the steps of examining cache entries of known peer address certificates to determine appropriate nodes to which to send a resolution request, randomly selecting one of the appropriate nodes, and sending the resolution request to the randomly selected node. In one embodiment the step of randomly selecting one of the appropriate nodes comprises the step of calculating a weighted probability for each of the appropriate nodes based on the distance of the PNRP ID from the target ID. The probability of choosing a specific next hop is then determined as an inverse proportionality to the ID distance between that node and the target node.
In a further embodiment, a method of inhibiting a search based denial of service attack in a peer-to-peer network comprises the steps of receiving a RESPONSE message, determining if the RESPONSE message is in response to a prior RESOLVE message, and rejecting the RESPONSE message when the RESPONSE message is not in response to the prior RESOLVE message. Preferably, the step of determining if the RESPONSE message is in response to a prior RESOLVE message comprises the steps of calculating a bitpos as a hash of information in the RESPONSE message, and examining a bit vector to determine if a bit corresponding to the bitpos is set therein.
In one embodiment wherein the RESPONSE message contains an address list, the method further comprises the steps of determining if the RESPONSE message has been modified in an attempt to hamper resolution, and rejecting the RESPONSE message when the RESPONSE message has been modified in an attempt to hamper resolution. Preferably the step of determining if the RESPONSE message has been modified in an attempt to hamper resolution comprises the steps of calculating a bitpos as a hash of the address list in the RESPONSE message, and examining a bit vector to determine if a bit corresponding to the bitpos is set therein.
In another embodiment, a method of inhibiting a malicious node from removing a valid node from the peer-to-peer network comprises the steps of receiving a revocation certificate purportedly from the valid node having a peer address certificate (PAC) stored in the receiving node cache, and verifying that the revocation certificate is signed by the valid node.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram generally illustrating an exemplary computer system;
FIG. 2 is a simplified flow diagram illustrating security aspects of AUTHORITY packet processing;
FIG. 3 is a simplified communications processing flow diagram illustrating security aspects of a synchronization phase of P2P discovery;
FIG. 4 is a simplified flow diagram illustrating security aspects of RESOLVE packet processing;
FIG. 5 is a simplified flow diagram illustrating security aspects of FLOOD packet processing; and
FIG. 6 is a simplified flow diagram illustrating security aspects of RESPONSE packet processing.
While the following text includes certain preferred embodiments, there is no intent to limit it to those embodiments. On the contrary, the intent is to cover all alternatives, modifications and equivalents as included within the spirit and scope of the disclosure.
DETAILED DESCRIPTION
Turning to the drawings, wherein like reference numerals refer to like elements, an exemplary system for implementing the claims includes a suitable computing environment. Although not required, the patent will be described in the general context of computer-executable instructions, such as program modules, being executed by a personal computer. Generally, program modules include routines, programs, objects, components, data structures, etc. that perform particular tasks or implement particular abstract data types. Moreover, those skilled in the art will appreciate that the patent may be practiced with other computer system configurations, including hand-held devices, multi-processor systems, microprocessor based or programmable consumer electronics, network PCs, minicomputers, mainframe computers, and the like. The patent may also be practiced in distributed computing environments where tasks are performed by remote processing devices that are linked through a communications network. In a distributed computing environment, program modules may be located in both local and remote memory storage devices.
FIG. 1 illustrates an example of a suitable computing system environment 100 . The computing system environment 100 is only one example of a suitable computing environment and is not intended to suggest any limitation as to the scope of use or functionality of the patent. Neither should the computing environment 100 be interpreted as having any dependency or requirement relating to any one or combination of components illustrated in the exemplary operating environment 100 .
The patent is operational with numerous other general purpose or special purpose computing system environments or configurations. Examples of well known computing systems, environments, and/or configurations that may be suitable for use with the patent include, but are not limited to, personal computers, server computers, hand-held or laptop devices, multiprocessor systems, microprocessor-based systems, set top boxes, programmable consumer electronics, network PCs, minicomputers, mainframe computers, distributed computing environments that include any of the above systems or devices, and the like.
The patent may be described in the general context of computer-executable instructions, such as program modules, being executed by a computer. Generally, program modules include routines, programs, objects, components, data structures, etc. that perform particular tasks or implement particular abstract data types. The patent may also be practiced in distributed computing environments where tasks are performed by remote processing devices that are linked through a communications network. In a distributed computing environment, program modules may be located in both local and remote computer storage media including memory storage devices.
With reference to FIG. 1 , an exemplary system for implementing the patent includes a general purpose computing device in the form of a computer 110 . Components of computer 110 may include, but are not limited to, a processing unit 120 , a system memory 130 , and a system bus 121 that couples various system components including the system memory to the processing unit 120 . The system bus 121 may be any of several types of bus structures including a memory bus or memory controller, a peripheral bus, and a local bus using any of a variety of bus architectures. By way of example, and not limitation, such architectures include Industry Standard Architecture (ISA) bus, Micro Channel Architecture (MCA) bus, Enhanced ISA (EISA) bus, Video Electronics Standards Associate (VESA) local bus, and Peripheral Component Interconnect (PCI) bus also known as Mezzanine bus.
Computer 110 typically includes a variety of computer readable media. Computer readable media can be any available media that can be accessed by computer 110 and includes both volatile and nonvolatile media, removable and non-removable media. By way of example, and not limitation, computer readable media may comprise computer storage media and communication media. Computer storage media includes both volatile and nonvolatile, removable and non-removable media implemented in any method or technology for storage of information such as computer readable instructions, data structures, program modules or other data. Computer storage media includes, but is not limited to, RAM, ROM, EEPROM, flash memory or other memory technology, CD-ROM, digital versatile disks (DVD) or other optical disk storage, magnetic cassettes, magnetic tape, magnetic disk storage or other magnetic storage devices, or any other medium which can be used to store the desired information and which can be accessed by computer 110 . Communication media typically embodies computer readable instructions, data structures, program modules or other data in a modulated data signal such as a carrier wave or other transport mechanism and includes any information delivery media. The term “modulated data signal” means a signal that has one or more of its characteristics set or changed in such a manner as to encode information in the signal. By way of example, and not limitation, communication media includes wired media such as a wired network or direct-wired connection, and wireless media such as acoustic, RF, infrared and other wireless media. Combinations of the any of the above should also be included within the scope of computer readable media.
The system memory 130 includes computer storage media in the form of volatile and/or nonvolatile memory such as read only memory (ROM) 131 and random access memory (RAM) 132 . A basic input/output system 133 (BIOS), containing the basic routines that help to transfer information between elements within computer 110 , such as during start-up, is typically stored in ROM 131 . RAM 132 typically contains data and/or program modules that are immediately accessible to and/or presently being operated on by processing unit 120 . By way of example, and not limitation, FIG. 1 illustrates operating system 134 , application programs 135 , other program modules 136 , and program data 137 .
The computer 110 may also include other removable/non-removable, volatile/nonvolatile computer storage media. By way of example only, FIG. 1 illustrates a hard disk drive 141 that reads from or writes to non-removable, nonvolatile magnetic media, a magnetic disk drive 151 that reads from or writes to a removable, nonvolatile magnetic disk 152 , and an optical disk drive 155 that reads from or writes to a removable, nonvolatile optical disk 156 such as a CD ROM or other optical media. Other removable/non-removable, volatile/nonvolatile computer storage media that can be used in the exemplary operating environment include, but are not limited to, magnetic tape cassettes, flash memory cards, digital versatile disks, digital video tape, solid state RAM, solid state ROM, and the like. The hard disk drive 141 is typically connected to the system bus 121 through a non-removable memory interface such as interface 140 , and magnetic disk drive 151 and optical disk drive 155 are typically connected to the system bus 121 by a removable memory interface, such as interface 150 .
The drives and their associated computer storage media discussed above and illustrated in FIG. 1 , provide storage of computer readable instructions, data structures, program modules and other data for the computer 110 . In FIG. 1 , for example, hard disk drive 141 is illustrated as storing operating system 144 , application programs 145 , other program modules 146 , and program data 147 . Note that these components can either be the same as or different from operating system 134 , application programs 135 , other program modules 136 , and program data 137 . Operating system 144 , application programs 145 , other program modules 146 , and program data 147 are given different numbers hereto illustrate that, at a minimum, they are different copies. A user may enter commands and information into the computer 110 through input devices such as a keyboard 162 and pointing device 161 , commonly referred to as a mouse, trackball or touch pad. Other input devices (not shown) may include a microphone, joystick, game pad, satellite dish, scanner, or the like. These and other input devices are often connected to the processing unit 120 through a user input interface 160 that is coupled to the system bus, but may be connected by other interface and bus structures, such as a parallel port, game port or a universal serial bus (USB). A monitor 191 or other type of display device is also connected to the system bus 121 via an interface, such as a video interface 190 . In addition to the monitor, computers may also include other peripheral output devices such as speakers 197 and printer 196 , which may be connected through a output peripheral interface 195 .
The computer 110 may operate in a networked environment using logical connections to one or more remote computers, such as a remote computer 180 . The remote computer 180 may be another personal computer, a server, a router, a network PC, a peer device or other common network node, and typically includes many or all of the elements described above relative to the personal computer 110 , although only a memory storage device 181 has been illustrated in FIG. 1 . The logical connections depicted in FIG. 1 include a local area network (LAN) 171 and a wide area network (WAN) 173 , but may also include other networks. Such networking environments are commonplace in offices, enterprise-wide computer networks, intranets and the Internet.
When used in a LAN networking environment, the personal computer 110 is connected to the LAN 171 through a network interface or adapter 170 . When used in a WAN networking environment, the computer 110 typically includes a modem 172 or other means for establishing communications over the WAN 173 , such as the Internet. The modem 172 , which may be internal or external, may be connected to the system bus 121 via the user input interface 160 , or other appropriate mechanism. In a networked environment, program modules depicted relative to the personal computer 110 , or portions thereof, may be stored in the remote memory storage device. By way of example, and not limitation, FIG. 1 illustrates remote application programs 185 as residing on memory device 181 . It will be appreciated that the network connections shown are exemplary and other means of establishing a communications link between the computers may be used.
In the description that follows, the patent will be described with reference to acts and symbolic representations of operations that are performed by one or more computer, unless indicated otherwise. As such, it will be understood that such acts and operations, which are at times referred to as being computer-executed, include the manipulation by the processing unit of the computer of electrical signals representing data in a structured form. This manipulation transforms the data or maintains it at locations in the memory system of the computer, which reconfigures or otherwise alters the operation of the computer in a manner well understood by those skilled in the art. The data structures where data is maintained are physical locations of the memory that have particular properties defined by the format of the data. However, while the patent is being described in the foregoing context, it is not meant to be limiting as those of skill in the art will appreciate that various of the acts and operation described hereinafter may also be implemented in hardware.
As introduced above, the success of a peer-to-peer (P2P) protocol depends on the protocol's ability to establish valid connections between selected entities. Because a particular user may connect to the network in various ways at various locations having different addresses, a preferred approach is to assign a unique identity to the user, and then resolve that identity to a particular address through the protocol. Such a peer-to-peer name resolution protocol (PNRP) to which the security infrastructure of the patent finds particular applicability is described in co-pending application Ser. No. 09/942,164, entitled Peer-To-Peer Name Resolution Protocol (PNRP) And Multilevel Cache For Use Therewith, filed on Aug. 29, 2001, the teachings and disclosure of which are hereby incorporated in their entireties by reference thereto. However, one skilled in the art will recognize from the following teachings that the security infrastructure and methods are not limited to the particular peer-to-peer protocol of this co-pending application, but may be applied to other protocols with equal force.
As discussed in the above-incorporated co-pending application, the peer name resolution protocol (PNRP) is a peer-based name-to-address resolution protocol. Names are 256-bit numbers called PNRP IDs. Addresses consist of an IPv4 or IPv6 address, a port, and a protocol number. When a PNRP ID is resolved into an address, a peer address certificate (PAC) is returned. This certificate includes the target's PNRP ID, current IP address, public key, and many other fields. An instance of the PNRP protocol is called a node. A node may have one or more PNRP IDs registered locally. A node makes an ID-to-address mapping discoverable in PNRP via registration. Each registration includes a locally constructed peer certificate, and requires an appropriate view of the PNRP cache. Hosts which are not PNRP nodes may resolve PNRP IDs into IP addresses via a PNRP DNS gateway. A PNRP DNS gateway accepts DNS ‘A’ and ‘AAAA’ queries, performs a PNRP search for a subset of the hostname specified, and returns the results as a DNS query answer.
As indicated above, PNRP provides a peer-based mechanism associating P2P and PNRP IDs with peer address certificates (PACs). A P2P ID is a persistent 128-bit identifier. P2P IDs are created by hashing a correctly formatted P2P name. There are two types of P2P IDs, secure and insecure. A secure P2P ID is an ID with a verifiable relationship to a public key. An insecure P2P ID is any ID which is not secure. A given P2P ID may be published by many different nodes. PNRP uses a ‘service location’ suffix to ensure each published instance has a unique PNRP ID. A ‘service location’ is a 128-bit number corresponding to a unique network service endpoint. Service locations have some recognizable elements, but should be considered opaque by PNRP clients. A service location has two important properties. At any moment, only one socket in the cloud corresponds to a given service location. When two service locations are compared, the length of the common prefix for each is a reasonable measure of network proximity. Two service locations which start with the same four bits are no further apart than two which start with the same three bits.
A P2P ID is uniquely identified by its catenation with the service location. The resulting 256-bit (32 byte) identifier is called a PNRP ID. PNRP nodes register a PNRP ID by invoking PNRP services with a P2P name, authority, and several other parameters. PNRP services then creates and maintains a Peer Address Certificate (PAC) containing the submitted data. PACs include at a minimum a PNRP ID, certificate validity interval, service and PNRP address, public key, and a cryptographic signature generated over select PAC contents.
Creation and registration of PNRP IDs is only one part of the PNRP service. The PNRP service execution can be divided into four phases. The first is PNRP cloud discovery. During this phase a new node must find an existing node in the cloud it wishes to join. The cloud may be the global PNRP cloud, a site local (enterprise) cloud, or a link local cloud. Once found, the second phase of joining a PNRP cloud is entered. Once the new node has found an existing node, it performs a SYNCHRONIZE procedure to obtain a copy of the existing node's top cache level. A single cache level provides enough basis for a new node to start participating in the cloud. Once the SYNCHRONIZATION has been achieved, the next phase, active participation in the cloud, may be begun. After initialization has completed, the node may participate in PNRP ID registration and resolution. During this phase, the peer also performs regular cache maintenance. When the node is done, it enters the fourth phase, leaving the cloud. The node un-registers any locally registered PNRP IDs, then terminates.
The PNRP protocol consists of nine different types of packets, some of which have been introduced above. It should be noted, however, that in this application the names of the packets are used merely to facilitate an understanding of their functionality, and should not be taken as limiting the form or format of the packet or message itself. The RESOLVE packet requests resolution of a target PNRP ID into a PAC. A RESPONSE packet is the result of a completed RESOLVE request. The FLOOD packet contains a PAC intended for the PNRP cache of the recipient. A SOLICIT packet is used to ask a PNRP node to ADVERTISE its top level cache. The requested ADVERTISE packet contains a list of PNRP IDs for PACs in a node's top level cache. A REQUEST packet is used to ask a node to flood a subset of ADVERTISE'd PACs. An INQUIRE packet is used to insecurely ask a node whether a specific PNRP ID is registered at that node. To confirm local registration of a PNRP ID, an AUTHORITY packet is used. This packet optionally provides a certification chain to help validate the PAC for that ID. An ACK packet acknowledges receipt and/or successful processing of certain messages. Finally, the REPAIR packet is used to try to merge clouds that may be split.
Once a node is fully initialized, it may participate in the PNRP cloud by performing five types of activities. First, a node may register and un-register PNRP IDs. When a PNRP ID is registered, the PNRP service creates a peer address certificate (PAC) associating the PNRP ID, service address port and protocol, PNRP address port and protocol, and a public key. This PAC is entered into the local cache, and a RESOLVE is initiated using the new PAC as the source, and [PNRP ID+1] as the target. This RESOLVE is processed by a number of nodes with PNRP IDs very similar to the registered ID. Each recipient of the RESOLVE adds the new node's PAC to their cache, thereby advertising the new PNRP ID in the cloud. When a PNRP ID is un-registered, an updated PAC is created with a ‘revoke’ flag set. The updated PAC is flooded to all entries in the lowest level of the local cache. Each recipient of the FLOOD checks its cache for an older version of the PAC. If one is found, the recipient removes the PAC from its cache. If the PAC is removed from the lowest cache level, the recipient in turn FLOODs the revocation to the PNRP nodes represented by all other PACs in its lowest cache level.
The PNRP node may also participate in PNRP ID resolution. As discussed in the above incorporated application, PNRP IDs are resolved into PACs by routing RESOLVE messages successively closer to the target PNRP ID. When a node receives a RESOLVE, it may reject the RESOLVE back to the previous hop, respond to the previous hop with a RESPONSE, or forward the RESOLVE to a node whose PNRP ID is closer to the target ID than the node's own. The node also receives and forwards RESPONSE packets as part of resolution. The PNRP node may also initiate RESOLVEs on behalf of a local client. The PNRP service provides an API to allow asynchronous resolution requests. The local node originates RESOLVE packets, and eventually receives a corresponding RESPONSE.
The PNRP node also honors cache synchronization requests. Upon receiving a SOLICIT packet, the node responds with an ADVERTISE packet, listing the PNRP IDs in its highest cache level. The solicitor node then sends a REQUEST listing the PNRP IDs for any ADVERTISE'd PACs it wants. Each REQUESTed cache entry is then FLOODed to the REQUESTor. Finally, and as will be discussed more fully below, the PNRP also performs identity validation. Identity validation is a threat mitigation device used to validate PACs. Identity validation basically has two purposes. First, identity validation ensures that the PNRP node specified in a PAC has the PNRP ID from that PAC locally registered. Second, for secure PNRP IDs (discussed below), identity validation ensures that the PAC was signed using a key with a cryptographically provable relationship to the authority in the PNRP ID.
Having now provided a working knowledge of the PNRP system for which an embodiment of the security infrastructure finds particular relevance, attention is now turned to the security mechanisms provided by the security infrastructure. These mechanisms are provided to eliminate, or at a minimum mitigate, the effect of the various attacks that may be posed by a malicious node in a P2P cloud as discussed above. The PNRP protocol does not have any mechanism to prevent these attacks, nor is there a single solution to address all of these threats. The security infrastructure, however, minimizes the disruption that may be caused by a malicious node, and may be incorporated into the PNRP protocol.
As with many successful P2P protocols, entities can be published for easy discovery. To provide security and integrity to the P2P protocol, however, each identity preferably includes an attached identity certificate. However, a robust security architecture will be able to handle both secure and insecure entities. This robustness is provided through the use of self-verifying PACs.
A secure PAC is made self-verifying by providing a mapping between the ID and a public key. This will prevent anyone from publishing a secure PAC without having the private key to sign that PAC, and thus will prevent a large number of identity theft attacks. The keeper of the ID private key uses the certificate to attach additional information to the ID, such as the IP address, friendly name, etc. Preferably, each node generates its own pair of private-public keys, although such may be provided by a trusted supplier. The public key is then included as part of the node identifier. Only the node that created the pair of keys has the private key with which it can prove that it is the creator of the node identity. In this way, identity theft may be discovered, and is, therefore, deterred.
A generic format for such certificates may be represented as [Version, ID, <ID Related Info>, Validity, Algorithms, P.sub.Issuer]K.sub.Issuer. Indeed, P2P name/URL is part of the basic certificate format, regardless of whether it is a secure or insecure ID. As used in this certificate representation, Version is the certificate version, ID is the identifier to be published, <ID Related Info> represents information to be associated with the ID, Validity represents the period of validity expressed in a pair of From-To dates expressed as Universal Date Time (aka GMT), Algorithms refers to the algorithms used for generating the key pairs, and for signing, and P.sub.Issuer is the public key of the certificate issuer. If the certificate issuer is the same as the ID owner then this is P.sub.ID the public key of the ID owner. The term K.sub.Issuer is the private key corresponding to P.sub.Issuer. If the certificate issuer is the ID owner then this is K.sub.ID, the private key of the ID owner.
In a preferred embodiment, the <ID related info> comprises the address tuple where this ID can be found, and the address tuple for the PNRP service of the issuer. In this embodiment, the address certificate becomes [Version, ID, <Address>.sub.ID, <Address>.sub.PNRP, Validity, Revoke Flag, Algorithms, P.sub.Issuer]K.sub.Issuer. In this expanded representation, the ID is the identifier to be published, which can be a Group ID or Peer ID. The <Address> is the tuple of IPv6 address, port, and protocol. <Address>.sub.ID is the address tuple to be associated with the ID. <Address>.sub.PNRP is the address tuple of the PNRP service (or other P2P service) on the issuer machine. This is preferably the address of the PNRP address of the issuer and will be used by the other PNRP nodes to verify the validity of the certificate. Validity is the period of validity expressed in a pair of From-To dates. The Revoke Flag, when set, marks a revocation certificate. The P.sub.Issuer is the public key of the certificate issuer, and the K.sub.Issuer is the private key corresponding to P.sub.Issuer. If the certificate issuer is the ID owner then this is K.sub.ID, the private key of the ID.
In one embodiment, the following conditions have to be met for a certificate to be valid. The certificate signature must valid, and the certificate cannot be expired. That is, the current date expressed as UDT must be in the range specified by the Validity field. The hash of the public key must also match the ID. If the Issuer is the same as the ID owner then the hashing of the issuer's public key into the ID has to verify. If the P.sub.Issuer is different from P.sub.ID then there must be a chain of certificates leading to a certificate signed with K.sub.ID. Such a chain verifies the relationship between the issuer and the ID owner. Additionally, in the case when a certification revocation list (CRL) is published for that class of IDs and the CRL is accessible, then the authenticator can verify that none of the certificates in the chain appear in the CRL.
The security infrastructure also handles insecure PACs. An insecure PAC is made self-verifying by including the uniform resource identifier (URI) from which the ID is derived. Indeed, both secure and insecure IDs include the URI in the PAC. The URI is of the format “p2p://URI”. This will prevent a malicious node from publishing another node's secure ID in an insecure PAC.
The security infrastructure also allows for the use of insecure IDs. The problem with insecure IDs is that they are very easy to forge: a malicious node can publish an insecure ID of any other node. Insecure IDs also open security holes wherein it becomes possible to make discovery of a good node difficult. However, by including a URI, the insecure IDs cannot affect the secure IDs in any way. Further, the infrastructure requires that the PACs containing insecure IDs be in the same format as secure PACs, i.e. they contain public key and private keys. By enforcing the same structure on both insecure PACs and secure PACs, the bar for generating PACs is not lowered. Further, by including a URI in the PAC it is not computationally feasible to generate a URI that maps to a specific secure ID.
One issue that arises is the timing of PAC verification, recognizing a trade off between increased P2P cloud security and increased overhead. The PAC contained in the various packets discussed above has to be verified at some point, however. This PAC verification includes checking the ID signature validity and checking if the ID corresponds to the public key for secure IDs. To balance the overhead versus security issues, one embodiment verifies the PACs before any processing of that packet is done. This ensures that invalid data is never processed. However, recognizing that PAC verification may slow down the packet processing, which might not be suitable for certain classes of packets (e.g. RESOLVE packets), an alternate embodiment does not verify the PAC in these packets.
In addition to PAC verification, the security also performs an ID ownership check to validate the PAC. As discussed above, identity theft can be discovered by simple validation of the address certificate before using that address in PNRP or other P2P protocols. This validation may entail simply verifying that the ID is the hash of the public key included in the certificate. The ownership validation may also entail the issuance of an INQUIRE packet to the address in that PAC. The INQUIRE packet will contain the ID to be verified, and a transaction ID. If the ID is present at that address, the node should acknowledge that INQUIRE. If the ID is not present at that address, the node should not acknowledge that INQUIRE. If the certificate chain is required to verify the identity, the node returns the complete certificate chain. While signature and ID->URL validation is still complex and a significant use of resources, as is validating the chain of trust in a supplied cert chain, the system avoids any sort of challenge/response protocol, which would add an additional level of complexity to PAC validation. Further, the inclusion of the transaction ID prevents the malicious node from pre-generating the response to the INQUIREs. Additionally, this mechanism dispenses with the requirement that the PAC carry the complete certificate chain.
The ID ownership check is also facilitated in the system by modifying the standard RESOLVE packet so that it can also perform the ID ownership check. This modified RESOLVE packet contains the ID of the address to which the RESOLVE is being forwarded. If the ID is at that address, it will send an ACK, otherwise it will send a NACK. If the ID does not process the RESOLVE or if a NACK is received, the ID is removed from the cache. In this way a PAC is validated without resorting to any sort of challenge/response protocol and without sending any special INQUIRE packet by, in essence, piggybacking an INQUIRE message with the RESOLVE. This piggybacking process will be discussed again below with respect to FIG. 2 . This procedure makes it easy to flush out invalid or stale PACs.
This identity validation check happens at two different times. The first is when a node adds a PAC to one of its lowest two cache levels. PAC validity in the lowest two cache levels is critical to PNRP's ability to resolve PNRP IDs. Performing identity validation before adding a PAC to either of these two levels mitigates several attacks. ID ownership is not performed if the PAC is added to any higher level cache because of the turnover in these higher levels. It has been determined that nearly 85% of all PAC entries in the higher levels of cache are replaced or expire before they are ever used. As such, the probability of seeing any effect from having an invalid PAC in these higher levels is low enough not to justify performing the ID validation when they are entered.
When it is determined that an entry would belong in one of the two lowest cache levels, the PAC is placed in a set aside list until its identity can be validated. This first type of identity validation uses the INQUIRE message. Such an identity validation confirms a PAC is still valid (registered) at its originating node, and requests information to help validate authority of the originating node to publish that PAC. One flag in the INQUIRE message is defined for the ‘flags’ field, i.e. RF_SEND_CHAIN, that requests the receiver to send a certificate chain (if any exists) in an AUTHORITY response. If the receiver of the INQUIRE does not have authority to publish the PAC or if the PAC is no longer locally registered, the receiver simply drops the INQUIRE message. Since the local node does not receive a proper response via an AUTHORITY message, the bad PAC will never be entered into its cache, and therefore can have no malicious effect on its operation in the P2P cloud.
If the receiver of the INQUIRE does have the authority to issue the PAC and if it is still locally registered, that node will respond 200 to the INQUIRE message with an AUTHORITY message as illustrated in FIG. 2 . While not illustrated in FIG. 2 , the receiving node in an embodiment checks to see if the AUTHORITY message says that the ID is still registered at the node which sent the AUTHORITY. Once the local node determines 202 that this AUTHORITY message is in response to the INQUIRE message, it removes the PAC from the set aside list 204 . If the certificate chain was requested 206 , the AUTHORITY message is checked to see if the certificate chain is present and valid 208 . If the certificate chain is present and valid, then the PAC is added to the cache and marked as valid 210 . Otherwise, the PAC is deleted 212 . If the certificate chain was not requested 206 , then the PAC is simply added to the cache and marked as valid 210 .
As may now be apparent, this AUTHORITY message is used to confirm or deny that a PNRP ID is still registered at the local node, and optionally provides a certificate chain to allow the AUTHORITY recipient to validate the node's right to publish the PAC corresponding to the target ID. In addition to the INQUIRE message, the AUTHORITY message may be a proper response to a RESOLVE message as will be discussed below. The AUTHORITY message includes various flags that may be set by the receiving node to indicate a negative response. One such flag is the AF_REJECT_TOO_BUSY flag, which is only valid in response to a RESOLVE. This flag indicates that the host is too busy to accept a RESOLVE, and tells the sender that it should forward the RESOLVE elsewhere for processing. While not aiding in the identity validation, it is another security mechanism to prevent a DoS attack as will be discussed more fully below. The flag AF_INVALID_SOURCE, which is only valid in response to a RESOLVE, indicates that the Source PAC in the RESOLVE is invalid. The AF_INVALID_BEST_MATCH flag, which is also only valid in response to a RESOLVE, indicates that the ‘best match’ PAC in the RESOLVE is invalid. The AF_UNKNOWN_ID flag indicates that the specified ‘validate’ PNRP ID is not registered at this host. Other flags in the AUTHORITY message indicate to the receiving node that requested information is included. The AF_CERT_CHAIN flag indicates that a certificate chain is included that will enable validation of the relationship between the ‘validate’ PNRP ID and the public key used to sign the PAC. The AUTHORITY message is only sent as an acknowledgement/response to either the INQUIRE or RESOLVE messages. If an AUTHORITY is ever received out of this context, it is discarded.
The second time that identity validation is performed is opportunistically during the RESOLVE process. As discussed, PNRP caches have a high rate of turnover. Consequently, most cache entries are overwritten in the cache before they are ever used. Therefore, the security infrastructure does not validate these PACs until and unless they are actually used. When a PAC is used to route a RESOLVE path, the system piggybacks identity validation on top of the RESOLVE packet as introduced above. The RESOLVE contains a ‘next hop’ ID which is treated the same as the target ID in an INQUIRE packet. This RESOLVE is then acknowledged with an AUTHORITY packet, the same as is expected for an INQUIRE discussed above. If an opportunistic identity validation fails, the receiver of the RESOLVE is not who the sender believes they are. Consequently, the RESOLVE is routed elsewhere and the invalid PAC is removed from the cache.
This process is also illustrated in FIG. 2 . When a PNRP node P receives an AUTHORITY packet 200 with the header Message Type field set to RESOLVE 202 , the receiving node examines the AUTHORITY flags to determine if this AUTHORITY flag is negative 214 , as discussed above. If any of the negative response flags are set in the AUTHORITY message, the PAC is deleted 216 from the cache and the RESOLVE is routed elsewhere. The address to which the RESOLVE was sent is appended to the RESOLVE path and marked REJECTED. The RESOLVE is then forwarded to a new destination. If the AUTHORITY is not negative and if the certificate chain was requested 218 , the AUTHORITY message flag AF_CERT_CHAIN is checked to see if the certificate chain is present. If it is present the receiving node should perform a chain validation operation on the cached PAC for the PNRP ID specified in validate. The chain should be checked to ensure all certificates in it are valid, and the relationship between the root and leaf of the chain is valid. The hash of the public key for the chain root should, at a minimum, be compared to the authority in the PACs P2P name to ensure they match. The public key for the chain leaf should be compared against the key used to sign the PAC to ensure they match. If any of these checks fail or if the certificate chain is not present when requested 220 , the PAC should be removed from the cache 222 and the RESOLVE reprocessed. If the requested certificate chain is included and is validated 220 , the PAC corresponding to the validate PNRP ID should be marked as fully validated 224 . If desired, the PNRP ID, PNRP service address, and validation times may be retained from the PAC and the PAC itself deleted from the cache to save memory.
As an example of this identity validation, assume that ‘P’ is a node requesting an identity validation for PNRP ID ‘T’. ‘N’ is the node receiving the identity validation request. This could happen as a result of P receiving either an INQUIRE packet with target ID=T, or a RESOLVE packet with next hop=T. N checks its list of PNRP IDs registered locally. If T is not in that list, then the received packet type is checked. If it was an INQUIRE, N silently drops the INQUIRE request. After normal retransmission attempts expire, P will discard the PAC as invalid and processing is done. If it was a RESOLVE, N responds with an AUTHORITY packet indicating ID T is not locally registered. P then sends the RESOLVE elsewhere. If T is in the list of PNRP IDs at N, N constructs an AUTHORITY packet and sets the target ID to T. If T is an insecure ID, then N sends the AUTHORITY packet to P. If T is a secure ID, and the authority for the secure ID is the key used to sign the PAC, then N sends the AUTHORITY packet to P. If neither of these are true and if the RF_SEND_CHAIN flag is set, then N retrieves the certificate chain relating the key used to sign the PAC to the authority for PNRP ID T. The certificate chain is inserted into the AUTHORITY packet, and then N sends the AUTHORITY packet to P. At this point, if T is an insecure ID processing is completed. Otherwise, P validates the relationship between the PAC signing key and the authority used to generate the PNRP ID T. If the validation fails, the PAC is discarded. If validation fails and the initiating message was a RESOLVE, P forwards the RESOLVE elsewhere.
As may now be apparent from these two times that identity ownership verification is performed, through either the INQUIRE or the modified RESOLVE packet, an invalid PAC cannot be populated throughout the P2P cloud using a FLOOD, and searches will not be forwarded to non-existent or invalid IDs. The PAC validation is necessary for FLOOD because, if the FLOOD packet is allowed to propagate in the network without any validation, then a DoS attack may result. Through these mechanisms, a popular node will not be flooded with ID ownership check because its ID will belong to only a very few nodes' lowest two cache levels.
As described more fully in the above referenced co-pending application, a PNRP node N learns about a new ID in one of four ways. It may learn of a new ID through the initial flooding of a neighbor's cache. Specifically, when a P2P node comes up it contacts another node member of the P2P cloud and initiates a cache synchronization sequence. It may also learn of a new ID as a result of a neighbor flooding a new record of its lowest cache. For example, assume that node N appears as an entry in the lowest level cache of node M. When M learns about a new ID, if the ID fits in its lowest level cache, it will flood it to the other entries in that cache level, respectively to N. A node may also learn of a new ID as a result of a search request. The originator of a search request inserts its address certificate in the request, and the PAC for the ‘best match’ to the search request so far also inserts its PAC into the request. In this way, all of the nodes along the search request path will update their cache with the search originator's address, and the best match's address. Similarly, a node may learn of a new ID as a result of a search response. The result of a search request travels a subset of the request path in reverse order. The nodes along this path update their cache with the search result.
According to PNRP, when the node first comes up it discovers a neighbor. As discussed above, however, if the node that is first discovered is a malicious node, the new node can be controlled by the malicious node. To prevent or minimize the possibility of such occurrence, the security infrastructure provides two mechanisms to ensure secure node boot up. The first is randomized discovery. When a node tries to discover another node that will allow it to join the PNRP cloud, the last choice for discovery is using multicast/broadcast because it is the most insecure discovery method of PNRP. Due to the nature of discovery it is very difficult to distinguish between a good and bad node. Therefore, when this multicast/broadcast method is required, the security infrastructure causes the node to randomly select one of the nodes who responded to the broadcast discovery message (MARCOPOLO or an existing multicast discovery protocol e.g., SSDP). By selecting a random node, the system minimizes the probability of selecting a malicious node. The system also performs this discovery without using any of its IDs. By not using IDs during discovery, the system prevents the malicious node from targeting a specific ID.
A second secure node boot up mechanism is provided by a modified sync phase during which the node will maintain a bit vector. This modified synch phase mechanism may best be understood through an example illustrated in the simplified flow diagram of FIG. 3 . Assume that Alice 226 sends a SOLICIT 228 to Bob 230 with her PAC in it. If Alice's PAC is not valid 232 , Bob 230 simply drops the SOLICIT 234 . If the PAC is valid, Bob 230 will then maintain a bit vector for storing the state of this connection. When this SOLICIT is received, Bob 230 generates 236 a nonce and hashes it with Alice's PNRP ID. The resulting number will be used as an index in this bit vector that Bob will set. Bob 230 then responds 238 to Alice 226 with an ADVERTISE message. This ADVERTISE will contain Bob's PAC and a nonce encrypted with Alice's public key, apart from other information, and will be signed by Bob 230 . When Alice 226 receives this ADVERTISE, she verifies 240 the signature and Bob's PAC. If it cannot be verified, it is dropped 241 . If it can be verified, Alice 226 then decrypts 242 the nonce. Alice 226 will then generate 244 a REQUEST that will contain this nonce and Alice's PNRP ID. Bob 230 will process 246 this REQUEST by hashing Alice's PNRP ID with the nonce sent in the REQUEST packet. If 248 the bit is set in the bit vector having the hashed results as an index, then Bob will clear the bits and start processing the REQUEST 250 . Otherwise, Bob will ignore the REQUEST 252 as it may be a replay attack.
This makes the node boot up a secure process because the sequence cannot be replayed. It requires minimal overhead in terms of resources consumed, including CPU, network ports, and network traffic. No timers are required to be maintained for the state information, and only the ID that initiated the sync up will be sent data. Indeed, this modified sync phase is asynchronous, which allows a node to process multiple SOLICITs simultaneously.
Many of the threats discussed above can be minimized by controlling the rate at which the packets are processed, i.e. limiting node resource consumption. The idea behind this is that a node should not consume 100% of its CPU trying to process the PNRP packets. Therefore, in accordance with an embodiment a node may reject processing of certain messages when it senses that such processing will hinder its ability to function effectively.
One such message that the node may decide not to process is the RESOLVE message received from another node. This process is illustrated in simplified form in FIG. 4 . Once a RESOLVE message is received 254 , the node will check 256 to see if it is currently operating at a CPU capacity greater than a predetermined limit. If its CPU is too busy to process the RESOLVE message, it will send 258 an AUTHORITY message with the AF_REJECT_TOO_BUSY flag set indicating its failure to process the request because it is too busy. If the CPU is not too busy 256 , the node will determine 260 if all of the PACs in the RESOLVE message are valid, and will reject 262 the message if any are found to be invalid. If all of the PACs are valid 260 , the node will process 264 the RESOLVE.
If the node can respond 266 to the RESOLVE, the node will 268 convert the RESOLVE into a RESPONSE and send it to the node from which it received the RESOLVE. If, however, the target ID is not locally registered, the node will 270 calculate the bitpos as the hash of the fields in the RESOLVE and will set the corresponding bitpos in the bit vector. As discussed briefly above, this bit vector is used as a security mechanism to prevent the processing of erroneous reply messages when the node has not sent out any messages to which a reply is expected. The node finds the next hop to which to forward the RESOLVE, with the appropriate modifications to evidence its processing of the message. If 272 the node to which the RESOLVE is to be forwarded has already been verified, the node simply forwards 276 the RESOLVE to that next hop. If 272 this selected next hop has not yet been verified, the node piggybacks 274 an ID ownership request on the RESOLVE and forwards 276 it to that node. In response to the piggybacked ID ownership request, the node will expect to receive an AUTHORITY message as discussed above, the process for which is illustrated in FIG. 2 . As illustrated in FIG. 2 , if a validating AUTHORITY is not received at step 214 , the PAC of the node to which the RESOLVE was forwarded is deleted 216 from the cache and the RESOLVE is reprocessed from step 254 of FIG. 4 .
Another message that the node may decide not to process because its CPU is too busy is the FLOOD message. In this process, illustrated in simplified form in FIG. 5 , if 278 the new information present in the FLOOD goes to either of the lowest two cache levels, the PAC is checked to determine if it is valid 280 . If the PAC is not valid, the FLOOD is rejected 284 . However, if the PAC is valid 280 , it is put into a set-aside list 282 . The entries in the set-aside list are taken at random intervals and are processed when the CPU is not too busy. Since these entries are going to be entered in the lowest two levels of cache, both the ID verification and the ownership validation are performed as discussed above. If 278 the new information present in the FLOOD goes to the higher cache levels and the CPU is too busy to process them 286 , then they are discarded 288 . If the node has available CPU processing capacity 286 , the PAC is checked to determine if it is valid 290 . If it is, then the PAC is added to the cache 292 , otherwise the FLOOD is rejected 294 .
Node boot up (SYNCHRONIZE) is another process that consumes considerable resources at a node, including not only CPU processing capacity but also network bandwidth. However, the synchronization process is required to allow a new node to fully participate in the P2P cloud. As such, the node will respond to the request from another node for the boot up if it has enough available resources at the given time. That is, as with the two messages just discussed, the node may refuse to participate in the boot up if its CPU utilization is too high. However, since this process consumes so much capacity, a malicious node can still exploit this by launching a large number of such sequences. As such, an embodiment of the security infrastructure limits the number of node synchronizations that may be performed by a given node to prevent this attack. This limitation may additionally be time limited so that a malicious node cannot disable a node from ever performing such a synchronization again in the future.
Also discussed above were many search based attacks that could be launched or caused by a malicious node. To eliminate or minimize the effect of such search based attacks, the system provides two mechanisms. The first is randomization. That is, when a node is searching for an appropriate next hop to which to forward a search request (RESOLVE), it identifies a number of possible candidate nodes and then randomly selects one ID out of these candidate IDs to which to forward the RESOLVE. In one embodiment, three candidate nodes are identified for the random selection. The IDs may be selected based on a weighted probability as an alternative to total randomization. One such method of calculating a weighted probability that the ID belongs to a non-malicious node is based on the distance of the PNRP ID from the target ID. The probability is then determined as an inverse proportionality to the ID distance between that node and the target node. In any event, this randomization will decrease the probability of sending the RESOLVE request to a malicious node.
The second security mechanism that is effective against search based attacks utilizes the bit vector discussed above to maintain state information. That is, a node maintains information identifying all of the RESOLVE messages that it has processed for which a response has not yet been received. The fields that are used to maintain the state information are the target ID and the address list in the RESOLVE packet. This second field is used to ensure that the address list has not been modified by a malicious node in an attempt to disrupt the search. As discussed above with the other instances of bit vector use, the node generates a hash of these fields from the RESOLVE and sets the corresponding bitpos in the bit vector to maintain a history of the processing of that RESOLVE.
As illustrated in the simplified flow diagram of FIG. 6 , when a RESPONSE message is received 296 from another node, the fields in this RESPONSE message are hashed 298 to calculate the bitpos. The node then checks 300 the bit vector to see if the bitpos is set. If the bit is not set, meaning that this RESPONSE is not related to an earlier processed RESOLVE, then the packet is discarded 302 . If the bitpos is set, meaning that this RESPONSE is related to an earlier processed RESOLVE, the bitpos is reset 304 . By resetting the bitpos, the node will ignore further identical RESPONSE messages that may be sent as part of a playback attack from a malicious node. The node then checks to make sure that all of the PACs in the RESPONSE message are valid 306 before processing the RESPONSE and forwarding it to the next hop. If any of the PACs are invalid 306 , then the node will reject 310 the packet.
The RESOLVE process mentions converting a RESOLVE request into a RESPONSE. This RESPONSE handling just discussed involves ensuring the RESPONSE corresponds to a recently received RESOLVE, and forwarding the RESPONSE on to the next hop specified. As an example, assume that node P receives a RESPONSE packet S containing a target PNRP ID, a BestMatch PAC, and a path listing the address of all nodes which processed the original RESOLVE before this node, ending with this node's own PNRP address. Node P acknowledges receipt of the RESPONSE with an ACK. Node P checks the RESPONSE path for its own address. Its address must be the last entry in the address list for this packet to be valid. Node P also checks its received bit vector to ensure that the RESPONSE matches a recently seen RESOLVE. If the RESPONSE does not match a field in the received bit vector, or if P's address is not the last address in the path list, the RESPONSE is silently dropped, and processing stops. P validates the BestMatch PAC and adds it to its local cache. If the BestMatch is invalid, the RESPONSE is silently dropped, and processing stops. P removes its address from the end of the RESPONSE path. It continues removing entries from the end of the RESPONSE path until the endmost entry has a flag set indicating a node that ACCEPTED the corresponding RESOLVE request. If the path is now empty, the corresponding RESOLVE originated locally. PNRP does an identity validation check on the BestMatch. If the identity validation check succeeds, the BestMatch is passed up to the request manager, else a failure indication is passed up. If the path is empty, processing is complete. If the path is not empty, the node forwards the RESPONSE packet to the endmost entry in the path list.
A need for a PNRP address certificate revocation exists whenever the published address certificate becomes invalid prior to the certificate expiration date (Validity/To field). Examples of such events are when a node is gracefully disconnecting from the P2P network, or when a node is leaving a group, etc. The revocation mechanism utilizes the publishing of a revocation certificate. A revocation certificate has the Revoke Flag set, and the From date of the Validity field set to the current time (or the time at which the certificate is to become revoked) and the To field set to the same value as the previously advertised certificates. All the certificates for which all the following conditions are met are considered to be revoked: the certificate is signed by the same issuer; the ID matches the ID in the revocation certificate; the Address fields match the ones in the revocation certificate; the To date of the Validation field is the same as the To date of the Validation filed in the revocation certificate; and the From date of the Validation field precedes the From date of the Validation filed in the revocation certificate. Since the revocation certificate is signed, it ensures that a malicious node cannot disconnect anyone from the cloud.
The foregoing description of various embodiments has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the embodiments disclosed. Numerous modifications or variations are possible in light of the above teachings. The embodiments discussed were chosen and described to provide the best illustration of the disclosed principles and its practical application to thereby enable one of ordinary skill in the art to utilize the embodiments with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the disclosure as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally, and equitably entitled.
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A security infrastructure and methods are presented that inhibit the ability of a malicious node from disrupting the normal operations of a peer-to-peer network. The methods of the invention allow both secure and insecure identities to be used by nodes by making them self-verifying. When necessary or opportunistic, ID ownership is validated by piggybacking the validation on existing messages. The probability of connecting initially to a malicious node is reduced by randomly selecting to which node to connect. Further, information from malicious nodes is identified and can be disregarded by maintaining information about prior communications that will require a future response. Denial of service attacks are inhibited by allowing the node to disregard requests when its resource utilization exceeds a predetermined limit. The ability for a malicious node to remove a valid node is reduced by requiring that revocation certificates be signed by the node to be removed.
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This invention relates to a coupling member for an electrical connector.
Electrical connector assemblies are generally comprised of two separate housings, one housing having a plurality of contacts which are matable with a like plurality of contacts in the other housing when the housings are connected together. Typically, a rotatably mounted coupling ring would connect the two housings together. Previously, it has been known to provide an inner wall of the coupling ring and an outer wall of the receiving housing with threads and to captivate a flange of the coupling ring adjacent to a flange on one of the housings by one or more snap rings, rotation of the coupling ring thus drawing the two members together. In some applications, wherein an interconnection once form is not further disturbed, the formation of threads is an expensive feature not desired by a user. Further, thread formation is time consuming, prone to seizing and galling, often times must be lubricated and subject to wear. Also, in severe environmental conditions, a user sometimes desires to interconnect an assembly with speed and with great ease.
DISCLOSURE OF THE INVENTION
The invention is a one-piece coupling member for a connector assembly. The coupling member includes means for securing first and second electrical connector housings together and is characterized as tubular sleeve having opposite end faces, one end face having one or more fingers extending forwardly therefrom and the other end face having a plurality of resilient tabs extending radially inwardly therefrom, the fingers and tabs being integrally formed with the coupling member. Each of the fingers includes a hooked portion which defines an abutment shoulder that is received within an aperture of a flange on the first connector housing, the coupling member being mounted and dismounted to the first connector housing by deflecting the fingers radially inwardly and outwardly. Each of the tabs define retention means which are adapted to snap over a similar radial flange on the second electrical connector housing to which the coupling member is to be mounted.
In an another aspect, a tool having a pair of semi-circular plate portions is provided to remove the coupling member from the one housing. Each plate of the tool is hinged at one end face, thereby allowing the semi-circular faces of the plates to simultaneously press the fingers radially inwardly to deflect the hooked portion from engagement with the aperture and allow the coupling member to be removed from the one housing.
One advantage of the invention is a coupling member that reduces the number of parts and complexity of the interconnection necessary to mount a coupling member to an electrical connector housing.
Another advantage of the invention is a reduction in the assembly time necessary to mount a coupling member to a connector housing and a pair of connector housings together to form an electrical connector assembly.
Another advantage is simplicity by which a coupling member may be mounted to a connector housing and, alternately, be removed from the connector housing.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is an exploded perspective view of an electrical connector having a coupling member. FIG. 2 shows the coupling member of FIG. 1 assembled to an electrical connector housing member.
FIG. 3 shows, partially in section, the coupling member coupling a pair of electircal connector housings.
FIG. 4 shows detail of a tab uncoupling.
FIG. 5 shows detail of a finger uncoupling.
FIG. 6 shows a tool for uncoupling the coupling member of FIG. 3.
Referring now to the drawings, FIG. 1 illustrates a coupling member 30 according to the principles of this invention. The coupling member 30 is adapted to secure a first connector housing 10 to a second connector housing 20.
The first connector housing (i.e. a plug shell) 10 includes an engaging forward end portion 12 having a plurality of longitudinal keys 14, a non-engaging rearward end portion 16 and a radial flange 18 disposed medially of the plug end portions. Flange 18 includes a forward face 17 facing end portion 12 and a rearward face 19 facing end portion 16.
The second electrical connector housing (i.e. a receptacle shell) 20 includes an engaging forward end portion 22 having a plurality of longitudinal internal keyways 24, the keyways being adapted to receive the plug shell keys when the forward engaging end portions of the two connector members are mated, a non-engaging rearward end portion 26 and a radial flange 28 disposed medially of the receptacle end portions having an end face 29 facing end portion 26. Although shown best in FIG. 3, each connector housing 10, 20 would mount a plurality of mateable contacts 11, 21, for mating to complete an electrical connection between respective electrical wires 15, 25.
Preferably and in accord with this invention, coupling member 30 is formed of a thermoplastic and comprises a generally cylindrically shaped tubular sleeve 32 having a forward portion 34 and a rearward portion 36, these sleeve portions being adapted to telescopically fit about the engaging forward end portion 12, 22 of the first and second connector housings 10, 20 respectively. The outer diameter of radial flange 28 would preferably be of smaller diameter than the inner diameter of sleeve 32.
The forward portion 34 of coupling member 30 includes a radial inward support ring 38 having an exterior end face 40 and a plurality of resilient fingers 42 extending axially forward from end face 40 as cantilever-type beams, each finger having a distal end thereof being provided with a tapering surface 44 and a radial abutment shoulder 46 to thereby define a hooked portion 45. As shown, four fingers of generally rectangular cross-section are disposed substantially equiangularly around end face 40 of the coupling member. Radially disposed around and extending between the faces 17, 19 of radial flange 18 of the plug shell 10 are a plurality of generally rectangular openings 48, the openings being adapted to register with and receive the fingers 42 when inserted therethrough, each tapered surface 44 deflecting the hook portion 45 remotely of the finger downwardly to allow entry and each shoulder 46 being adapted to butt against the rear flange face 19 when the hook portion has passed through the opening to prevent unwanted withdrawal. The long dimension of the rectangular opening is generally radially disposed and provides a clearance fit for the finger.
At the rearward portion 36 of coupling member 30 and radially inwardly directed from the sleeve are, as shown in the embodiment, a pair of resiliently deflectable snap tabs 50. These snap tabs are adapted to be deflected (i.e. snapped) over radial flange 28 on the receptacle connector housing 20 and engage end face 29.
Although either of the electrical connector housings 10, 20 may be of metal, it is contemplated that for ease of fabrication and manufacturing costs, both of the electrical housings could be of a durable plastic material.
FIG. 2 shows coupling member 30 mounted onto plug shell 10 with the distal hooked portions 45 of each finger protruding from openings in the plug flange 18 and the shoulders butting against flange rear face 19 and thereby secure coupling member 30 to the plug shell.
FIG. 3 shows, partially in section, coupling member 30 mounted to plug shell 10 and coupled to receptacle shell 20. Also shown are pin-socket-type contacts 11, 21 mounted within dielectric inserts 13, 23 to interconnect their respective wires 15, 25. The inward support ring 38 is generally telescopically clearance fitted about the engaging forward end 12 of plug shell 10. The fingers 42 and hooked portions 45 extend through openings 48 such that radial shoulders 46 butt against rear flange face 19 and end face 40 is adjacent forward flange face 17 of radial flange 18. Also, resilient tabs 50 are shown received over radial flange 28 on receptacle shell 20 to engage flange end face 29 and thereby secure the receptacle end portion 22 in mated relationship with the plug end portion 12.
FIG. 4 shows detail of a tab being uncoupled from the receptacle. A user would radially compress rearward portion 36 of the sleeve 32, such as by squeezing inwardly on the coupling member, at locations generally 90° offset from the tabs, such compression causing the tab to deflect from engagement with the flange, whereby an axial force will allow the receptacle to be uncoupled from the coupling member.
FIG. 5 shows a resilient finger 42 being deflected radially inwardly such that the hooked portion 45 thereon disengages radial shoulder 46 from abutting relationship with the rearward face 19 of flange 18 to allow coupling member 30 to be removed from the plug shell. Preferably and to aid in finger deflection tapered surface 44 may be provided with a flat 44a for engagement by a release tool.
FIG. 6 shows a tool 60 for accomplishing the uncoupling of the coupling member fingers 42 from their securement to plug shell 10. Preferably and in accord with this invention, tool 60 comprises a pair of generally semi-circular plates 62, each plate having a semi-circular inner face 63, an outer face 65, and a pair of end faces 66, 68, the plates 62 being connected by a hinge 70 along their respective end faces 66. A clamping arm 67 is attached to the outer face 65 of each plate 62, the clamping arms serving to open or close the semi-circular plates 62 from open to closed positions, the closed position forcing semi-circular plates 62 and the respective end faces 68 towards one another, the plates 62 encircling hook portions 45 of the fingers 42, thus causing the hook-portions to radially compress.
OPERATION
A user would be provided with the plug and receptacle electrical connector housings 10, 20 and the coupling member 30 and the uncoupling tool 60. First the coupling member would be telescoped over and about the plug shell and the fingers 42 thrust through the flange openings 48, the openings forcing the fingers to radially deflect inwardly as the tapered surfaces 44 of the fingers enter the openings. After the hooked portions have been forced through the openings, the fingers snap radially outwardly to allow the radial shoulders 44 of the hook portions to engage the rearward face 19 of the flange 18. The receptacle member 20 would then be positioned so that the key 14 and keyways 24 line up and forced inwardly into the plug shell, full mated relationship occurring when tabs 50 have snapped over radial flange 28 of the receptacle housing.
To remove the assembly above mentioned, the receptacle connector would be forced outwardly of the coupling member by compressing about the sleeve 32 to deflect tabs 50 from enagement with flange 28. Next, the semi-circular plates 62 would be clamped radially downwardly about the flat on hook portions 45, forcing the hook portions radially downwardly and the shoulders from engagement with the radial flange, whereby the coupling member could be axially pulled from the plug connector and the connection removed.
While a preferred embodiment of this invention has been disclosed, it will be apparent to those skilled in the art, that changes may be made to the invention as set forth in the appended claims, and in some instances, certain features of the invention may be used to advantage without corresponding use of other features. Accordingly, it is intended that the illustrative and descriptive materials herein will be used to illustrate the principles of the invention and not to limit the scope thereof.
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A coupling member (30) includes four equiangularly spaced fingers (42) at one end and two deflectable tabs (50) at the other end which cooperate to couple a pair of connectors (10, 20) of the type having medial of their ends a flange (18, 28) one flange (18) being provided with four openings (48) for receiving the fingers therethrough and the other flange being of a smaller diameter than the sleeve inside diameter for receiving the tabs thereover, the coupling member telescoping over the connectors and causing the tabs to deflect over their flange (28) and the fingers to be radially deflected and abut their flange (18).
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is related to and claims priority to U.S. Provisional Application Ser. No. 60/406,345, filed Aug. 28, 2002. The entire contents of this prior application is incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed to a plasma processing apparatus and a method for using the apparatus to process substrates (e.g., semiconductor wafers or liquid crystal display panels), and in particular to the manufacture and use of an asymmetrical focus ring.
2. Discussion of the Background
As is known in the art, a fundamental step in the manufacture of semiconductor devices, such as integrated circuits (ICs), is the process of forming electrical interconnections. The formation of electrical circuits, such as semiconductor transistors, involves a series of steps starting with the formation of a blank silicon wafer. The blank silicon wafer is then processed using successive steps of depositing and etching away various materials to form the proper interconnections and therefore the electrical circuits.
One method of depositing and etching metal layers to and from a silicon wafer includes the use of a plasma reactor system. In semiconductor manufacturing, plasma reactor systems are used to remove material from or deposit material to a work-piece (e.g., semiconductor wafer) in the process of making integrated circuit (IC) devices. A key factor in obtaining the highest yield and overall quality of ICs is the uniformity of the etching and deposition processes.
In a narrow gap, high aspect ratio capacitively coupled plasma reactor, a multipurpose chuck assembly design is often employed that attempts to allow the chuck assembly (i.e. wafer work piece holder) to serve additional purposes other than supporting the wafer. The complexity of the mechanical design of the chuck assembly is such that a non-optimal vacuum system design is required. A vacuum pumping system is used to evacuate the reactor processing region to the low pressures necessary to create a clean environment, to which a specific gas chemistry is introduced, which provides an environment for the generation of plasma. Consequently, due to the complexity of the mechanical design of the chuck assembly, the symmetry of the vacuum system (relative to the wafer) is sacrificed such that the vacuum pump is usually positioned to access the reactor vacuum chamber from the side rather than from the chamber bottom or top.
This type of multi-purpose chuck assembly can become a very cumbersome component of the reactor. In a multi-purpose chuck assembly design, in addition to supporting the wafer, the chuck assembly is typically configured to provide vertical translation in order to reduce the electrode-to-wafer spacing. This spacing control is necessary in order to produce a narrow gap for process conditions and to enlarge the gap for wafer exchange. In addition to the aforementioned capabilities, the chuck typically sustains a radio frequency (RF) energy bias. Moreover, the chuck assembly design further includes components for chuck block cooling, electrostatic clamping, and backside gas flow to improve thermal conduction (between the wafer and the chuck). Consequently, the vacuum design is often a secondary consideration to other various mechanical and electrical component designs.
A reactor chamber that is equipped with a side mount vacuum port is considered an asymmetrical design in a nominally cylindrical system. An inherent drawback associated with an asymmetric design is that it often times produces an asymmetric process. One such asymmetry stemming from an asymmetric vacuum design is the observation of pressure field non-uniformity above the wafer when the chamber is evacuated from the side. That is, a pressure gradient with about 10-20% variation can occur across the wafer being processed. In general, for moderate to high pressures (e.g. P>20 mTorr), a region of low pressure is observed at an azimuthal location adjacent the pump entrance or pumping duct entrance (the pumping duct interfaces the inlet of the pump, e.g. turbo-molecular pump, with the vacuum chamber). In known capacitively-coupled plasma reactors, attempts to solve the problem of an asymmetric chamber flow field introduced by pumping from the side have included the insertion of an orifice plate adjacent to the chuck.
A processing chamber generally includes a single evacuated volume wherein a portion of that volume is proximate the wafer and is hereinafter referred to as the processing region. When an orifice plate is employed, the chamber volume is separated into two regions by the orifice plate. The first region is predominantly occupied by the wafer processing region and the second region, referred to as the pumping volume, is accessed by the vacuum pump. This solution tends to improve the flow-field uniformity in the upper chamber volume by providing sufficient flow resistance through the orifice plate. However, this improvement is achieved at the expense of flow conductance or pumping speed at the processing region. In addition to placing the orifice plate adjacent the chuck assembly, other known designs included locating the orifice plate adjacent other surfaces, e.g. any surface interfacing the processing chamber volume that allows the exhaust of chamber gases.
There are several inherent problems with the known methods that use an orifice plate to control pressure uniformity in a chamber. For example, known orifice plates typically distribute the small openings equally in the azimuthal direction about the orifice plate in the hope that the resultant flow conductance will be azimuthally symmetric through the plate. However, in order to achieve flow-field uniformity, it is necessary to restrict the flow through the orifice plate to the extent that the pressure difference across the orifice is significantly greater than any pressure gradient in the processing or pumping regions. This requires making the holes in the orifice plate small and, hence, paying a penalty in chamber pumping speed at the wafer. This penalty in pumping speed directly results in an adverse effect on throughput.
In addition to the problem of pressure field non-uniformity described above, an additional problem associated with plasma processing systems is the transport of plasma to the pumping duct and pump inlet. In general, the aforementioned orifice plate or a separate pumping duct screen is utilized to attenuate the plasma density prior to reaching the pump inlet. For example, in known systems a pump screen (with generally less than 50% solidity) is placed in the cross-section of the pumping duct. Unfortunately the pumping screen attenuates the plasma and also reduces the pumping speed delivered to the processing region by at least a factor of two. This approach results in at least 50% of the frontal area of the pumping duct cross-section being utilized for recombination surfaces. In conventional designs, there is a one-to-one relationship between the increase in recombination surface area and the decrease in the frontal (flow-through) area.
SUMMARY OF THE INVENTION
According to one aspect of the present invention, an asymmetrical focus ring varies the flow-field, which aids in normalizing pressure gradients across the wafer being processed, thereby improving the process. Embodiments of the present invention utilize a focus ring that either (1) contains a pattern of through holes that enhances pumping, or (2) does not contain any such pattern.
According to a second aspect, the position of the focus ring of the present invention may be adjusted by rotation on the centerline of the chuck assembly. This rotation allows further adjustment of pressure gradients in the chamber.
The focus rings of the present invention optionally may be utilized with an orifice plate or pumping plenum as an added method to adjust pressure gradients in the chamber. This pumping plenum also may rotate with the focus ring as a single unit.
A focus ring of the present invention may further utilize varying cross-sectional areas to restrict pumping flow in the chamber in varying amounts to reduce pressure gradients in the chamber.
By utilizing asymmetrical or varying geometries, the present invention, even when utilized without a pumping plenum, allows greater pumping speeds in the chamber than designs with a pumping plenum. The present invention also modifies the pressure gradient to a higher degree than designs where asymmetrical or varying cross sectional area focus rings are not used. This invention adds tailoring features to adjust vacuum pumping characteristics.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other advantages of the invention will become more apparent and more readily appreciated from the following detailed description of the exemplary embodiments of the invention taken in conjunction with the accompanying drawings, where:
FIG. 1 is a plan view of a portion of a plasma processing system (without a pumping plenum) using an asymmetric focus ring according to the present invention;
FIG. 2 is a cross-sectional side view of the plasma processing system of FIG. 1 ;
FIG. 3 is a plan view of a portion of a plasma processing system (without a pumping baffle) using an asymmetric focus ring containing holes according to the present invention;
FIG. 4 is a cross-sectional side view of the plasma processing system of FIG. 3 ;
FIG. 5 is a plan view of a portion of a plasma processing system (without a pumping plenum) using a symmetric focus ring with asymmetrical holes according to the present invention;
FIG. 6 is a plan view of a portion of a plasma processing system (with a pumping baffle) using an asymmetric focus ring containing holes according to the present invention;
FIG. 7 is a cross-sectional side view of the plasma processing system of FIG. 6 ; and
FIG. 8 is a cross-sectional side view of a plasma processing system using a variable cross-section focus ring.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to one aspect of the present invention, as shown in FIG. 1 , a plasma processing system 100 is provided that includes a process chamber 105 . Housed within the plasma process chamber 105 is a chuck assembly 110 for supporting a substrate during processing and a focus ring 120 which encircles an upper portion of the chuck assembly 110 . As illustrated, the focus ring 120 is asymmetric and includes a minor side 123 and a major side 126 . The major side 126 is provided closer to the pumping duct 130 that evacuates the plasma chamber 105 . For example, the minor side 123 can range from 0.5 to 2.5 cm in width, and the major side 126 can range from 2.5 to 10 cm in width.
The asymmetrical focus ring may be made from any number of materials (e.g., quartz, silicon, silicon carbide, carbon, ceramic or some dielectric or partially metal structure). In one embodiment of the present invention, the ring is made from a uniform surface roughness. In an alternate embodiment, the ring is made to have a varying surface roughness.
Without an asymmetrical focus ring, a region of low pressure is located adjacent to the pumping duct entrance. Accordingly, the asymmetrical focus ring 120 is constructed and placed in such a manner as to restrict flow in the area near the major side (i.e., in the area of the least pressure) of the process chamber 105 . Proceeding around the focus ring 105 in either direction away from the major side 126 , the restriction is lessened to a point where no restriction occurs near the minor side 123 (i.e., where pressure in the process chamber 105 is the highest). Furthermore the focus ring 120 is rotatable about a central axis of the chuck assembly 110 .
As shown in FIG. 2 , the focus ring 120 is held atop the chuck assembly 110 and opposite an upper electrode assembly 140 . The upper electrode assembly 140 may further include an impedance matching network (e.g., a fast match assembly). The chuck assembly 110 may be brought closer to the upper electrode 140 during processing and moved further away when the substrate is being exchanged. The movement may be controlled in conjunction with an automatic or robotic substrate transfer system (not shown).
According to an exemplary embodiment of the present invention shown in FIGS. 3 and 4 , an asymmetrical focus ring 120 is provided with a pattern of holes 129 to enhance pumping. The configuration of holes 129 may be other than as shown in the figures, but generally the configuration is selected to reduce pressure in the chamber 105 at the minor side 123 as compared to at the major side 126 .
Advantageously, the holes 129 in the focus ring 120 tend to confine a plasma to a processing volume versus significantly reducing pumping volume. This provides a good balance between pumping speed and uniformity which is lacking in known systems. Alternately, as shown in FIG. 5 , focus ring 120 can comprise a minor side 123 substantially equivalent in width to the major side 126 , wherein the asymmetry in design is introduced by the size of the holes distributed about the focus ring 120 . Alternately, the number density of holes can be varied about the focus ring 120 .
According to the exemplary embodiment of the present invention shown in FIGS. 6 and 7 , an orifice plate or pumping baffle is used in conjunction with focus ring 120 either containing throughholes or not. The focus ring 120 is arranged and located as before. The focus ring 120 is again rotatable, but the pumping baffle 150 rotates with the focus ring 120 as a unit. The pumping baffle 150 has a number of holes 155 to enhance pumping and aid in normalizing pressure gradients across the substrate under process. As with the holes 129 of the focus ring 120 , the holes 155 of the pumping baffle 150 can be configured other than as illustrated.
While the embodiments of FIGS. 1-7 have been illustrated as utilizing a focus ring 120 that has a substantially constant thickness, it is also possible to use a non-constant thickness as well. As shown in FIG. 8 , the focus ring 120 ′ still is generally configured to fit around the chuck assembly 110 within the process chamber 105 . The focus ring 120 ′, however, is constructed with cross-sectional areas varying around the periphery of the element. Generally cross-sections are constructed and placed in such a manner as to restrict the flow in the area of least pressure in the chamber (i.e., near where the major side 126 is placed). By varying the cross-section around the focus ring 120 ′ towards the minor side 123 , the variation in cross section (and therefore the variation in restriction) helps to enable uniform pumping in the process chamber 105 .
The focus rings 120 of FIGS. 1-8 can be retrofitted into existing process chambers 105 by exchanging the existing focus rings for the illustrated ones. By utilizing such focus rings, process chambers 105 also can be built without the added cost and complexity of a pumping baffle 150 . The focus ring 120 can be attached, affixed, or mounted to the chuck assembly using standard design practice for focus rings understood by those skilled in the art of plasma processing.
To improve uniformity, the focus ring 120 may also be equipped with a rotating attachment point. By turning the focus ring 120 using the rotating attachment point, the focus ring 120 is rotated about a centerline of the chuck assembly 110 . This enables the system 100 to alter a direction of the pressure gradient. A number of pressure sensing devices, such as pressure manometers, can be coupled to the outer wall of the process chamber 105 and configured to provide information on the spatial variation of the pressure field about the periphery of the processing region. Implementation of a number of pressure sensing devices is understood by one skilled in the art of vacuum system design.
Although only certain exemplary embodiments of this invention have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention.
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An asymmetrical focus ring varies the flow-field, which aids in normalizing pressure gradients across the wafer being processed, thereby improving the process. Embodiments of the present invention utilize a focus ring that either (1) contains a pattern of through holes that enhances pumping, or (2) does not contain any such pattern.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This patent application is a continuation in part of and claims priority to U.S. patent application Ser. No. 12/876,080, filed on Sep. 3, 2010, which claimed priority to then U.S. Provisional Patent Application Ser. No. 61/240,158, filed on Sep. 4, 2009.
TECHNICAL FIELD
The present novel technology relates generally to the field of mechanical engineering, and, more particularly, to a method and apparatus for preventing a back hoe bucket from digging beyond a predetermined depth or grade.
BACKGROUND
Keeping on grade while digging with a back hoe continues to be a challenge even for the most experienced operators. More so than most digging machines, the extended lever arm of the hoe combined with the downward digging forces applied to produce wiggling and vibration of the hoe arm and bucket. Even experienced operators, having developed a tactile ‘feel’ for how well the bucket is digging and cutting, have difficulty maintaining grade, and the more precisely grade must be maintained, the more difficult and draining the job. While very good operators are able to maintain grade reasonably well even over prolonged digging sessions, the job does take its toll both physically and mentally.
Conventional laser alignment and even GPS guided devices have been developed to give the operator more reliable feedback regarding how close the digging bucket is to the desired grade. Such devices provide feedback to the operator that the bucket is too high, too low, or on grade at any given time during the digging operation. However, the operator must still receive and manually respond to the feedback signals (up or down) provided by the devices. Such constant correction of the bucket depth has proven to be physically demanding and exhausting.
Thus, there is a need for a system for automatically preventing overdigging and for automatically keeping the excavation on a predetermined grade. The present novel technology addresses this need.
SUMMARY
The present novel technology relates to a method and apparatus for maintaining a predetermined grade while digging with a back hoe. One object of the present novel technology is to provide an improved means for generating laser lines. Related objects and advantages of the present novel technology will be apparent from the following description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a first embodiment of the present novel technology, a system for automatically maintaining a back hoe bucket on grade during a digging operation.
FIG. 2 is a perspective view of a second embodiment of the present novel technology, a system for automatically maintaining a back hoe bucket on grade during a digging operation.
FIG. 3 is a side elevation view of a first embodiment back hoe bucket of the resent novel technology.
FIG. 4A is a perspective view of the bucket of FIG. 2 having the contact member engaged.
FIG. 4B is a perspective view of the bucket of FIG. 2 having the contact member disengaged.
FIG. 5A is a top plan view of the bucket of FIG. 2 having the contact member engaged.
FIG. 5B is a top plan view of the bucket of FIG. 2 having the contact member disengaged.
FIG. 6A is a front elevation view of the bucket of FIG. 2 having the contact member engaged.
FIG. 6B is a front elevation view of the bucket of FIG. 2 having the contact member disengaged.
FIG. 7 is a schematic diagram of the process of FIG. 1 .
FIG. 8 a perspective view of a first embodiment system including an elongated bucket and interrupt bar assembly as connected to a skid loader.
FIG. 9A is a schematic view of the loader of FIG. 8 with the interrupt bar positioned away from the cutting edge of the bucket.
FIG. 9B is a schematic view of the loader of FIG. 8 with the interrupt bar moved toward a deployed position adjacent the cutting edge of the bucket.
FIG. 9C is a schematic view of the loader of FIG. 8 with the interrupt bar in a deployed position adjacent the cutting edge of the bucket.
FIG. 10 is a front perspective view of another embodiment back hoe bucket according to the system of FIG. 2 .
FIG. 11 is a partially cut away side elevation view of the bucket of FIG. 10 .
FIG. 12A is a rear perspective view of the bucket of FIG. 10 .
FIG. 12B is a partially cut away rear perspective view of the bucket of FIG. 10 .
FIG. 13 is an exploded perspective view of a third embodiment of the present novel technology, a kit for converting a standard hoe bucket into a bucket according to the embodiment of claim 1 or 2 .
FIG. 14A is a perspective view of a fourth embodiment of the present novel technology, and elongated bucket having an interrupt plate operationally connected thereto.
FIG. 14 B is a perspective view of the embodiment of FIG. 14A with the interrupt plate pivoted.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
For the purposes of promoting an understanding of the principles of the novel technology and presenting its currently understood best mode of operation, reference will now be made to the embodiments illustrated in the drawings and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the novel technology is thereby intended, with such alterations and further modifications in the illustrated device and such further applications of the principles of the novel technology as illustrated therein being contemplated as would normally occur to one skilled in the art to which the novel technology relates.
A first embodiment of the present novel technology is illustrated in FIGS. 1 and 3 - 9 C, a system 10 for automatically preventing a track hoe bucket, back hoe bucket, loader bucket, skid loader bucket or like bucket or shovel from digging substantially deeper than a predetermined grade depth parameter. While the following example and drawings focus on a hoe bucket, the claimed novel technology is not limited to a hoe system and includes other digging machines, such as front loaders and the like. The system 10 includes a position sensor 15 and a depth sensor 20 operationally connected to a microprocessor 25 and likewise connected in communication with a reference signal 30 . The sensors 15 , 20 may be separate, or may both be the same (such as a GPS transceiver). Further, some embodiments may only have a depth sensor 20 , while others may only have a position sensor 15 . The reference signal 30 may be from a GPS satellite, a laser, or the like.
The microprocessor 25 is also connected to an actuator assembly 37 . The actuator assembly typically 37 includes a pressure source or pump 40 , such as a hydraulic or pneumatic pump 40 is connected in fluidic communication with at least one hydraulic or pneumatic cylinder 45 . The hydraulic cylinder 45 is fixedly, and typically pivotably, connected to a hoe or shovel bucket or blade 50 having a cutting edge or teeth 53 . While actuator assembly 37 is described herein as being of the pressurized piston/cylinder type, actuator assembly 37 may likewise include other types of actuators, such as mechanical, electromechanical, or the like.
Bucket 50 is likewise connected to the distal portion of a hoe armature 51 . The hydraulic cylinder 45 is also operationally connected to an interrupt bar 55 , which is likewise pivotably connected to the bucket 50 . The position and depth sensors 15 , 20 are likewise operationally connected to the bucket 50 such that the depth of the bucket, and the cutting edge 53 , is either directly measured (such as by direct attachment of the sensor(s) 15 , to the bucket 50 ), or calculated (such as by connection of the sensor(s) 15 , 20 to a predetermined position on the distal portion of the armature 51 connected to the bucket 50 ).
In operation 100 , as schematically illustrated in FIG. 7 , microprocessor 25 is first programmed with the location and depth parameters of the grade or excavation to be dug 105 . The reference signal 30 is received 110 by the depth sensor 20 and/or microprocessor when the digging machine is in operation, and the depth of the bucket 50 is calculated in substantially real-time. The location of the bucket 50 is also typically calculated from information supplied by the location sensor 15 and received 115 by the microprocessor 25 . In some embodiments, the position sensor 15 may also be used to calculate the orientation of the bucket 50 , such as its degree of pivot relative to a predetermined base orientation, such as teeth down and parallel to the horizontal. The depth, location and orientation information are used to calculate the position of the bucket 50 and this is compared 120 by the microprocessor 25 to the programmed grade information. If the bucket 50 begins exceed 125 programmed grade parameters, such as moving deeper than the programmed grade, an actuation signal 130 , typically a voltage, is generated by the microprocessor 25 and sent to the hydraulic pump 40 , energizing the pump 40 and actuating the cylinder 45 to extend 145 and pivot the interrupt bar 55 into position to engage the ground ahead of the bucket 50 . This operation is shown sequentially in FIGS. 9A-9C , wherein the interrupt bar 55 connected to a skid loader bucket 50 is moved from a standby position ( FIG. 9A ) into an engaged position ( FIG. 9C ), preventing the bucket 50 from digging into the ground and, typically, slightly lifting the front end of the loader. If the bucket position does not exceed 135 the programmed grade parameters, a null signal 140 is sent to the pump 40 . Engagement of the ground by the interrupt bar 55 prevents the shovel or bucket 50 from penetrating deeper into the ground. The microprocessor 25 may then query the sensors 15 , 20 for bucket location information, and the cycle starts over. It should be noted that although the process of digging to grade is typically one of vertically removing dirt, the programmed grade may likewise be a substantially horizontal parameter, such as the walls of a dug basement. The microprocessor 25 may likewise combine vertical, horizontal, and/or bucket orientation parameters to govern the excavation of curved and/or complex shape surfaces.
The interrupt bar 55 is typically an elongated member made of a structural material, such as steel. The interrupt bar 55 is more typically rounded or generally cylindrical. The interrupt bar 55 is generally U-shaped, having an elongated and generally rounded middle portion 70 and parallel connection members 75 extending from either end of the middle portion at generally right angles from the axis of the middle portion 70 . The middle portion 70 and connection members 75 may define a unitary piece (see FIGS. 10-12B ), or may be connected together as separate pieces.
FIG. 2 illustrates one specific configuration of the system 10 wherein a single hydraulic cylinder 45 is used to pivot the interrupt bar 55 , while FIGS. 3-9C illustrate a configuration wherein a pair of cylinders 45 are used. The cylinders 45 are illustrated as positioned in the interior of the bucket 50 , but may likewise be positioned adjacent the exterior of the bucket 50 .
FIGS. 10-12B illustrate a variation of the bucket 50 illustrated in FIG. 2 and discussed above, wherein the interrupt bar 55 and piston-cylinder actuator 45 are enclosed in a recess 200 formed in the bucket 50 . In this embodiment, the recess 200 is defined by inner bucket wall 205 and outer bucket wall 201 which create the double-walled bottom portion or recess 200 . The actuator 45 is positioned in the recess 200 and is fixedly mounted to the bucket 50 at one end and to the interrupt bar 55 at the other. Energization of the actuator 45 advances the interrupt bar 55 out of the recess 200 to a position adjacent the cutting edge 53 , where it is interposed between the bucket 50 and the ground. Bottom wall 210 acts to protect the actuator 45 from clogging by dirt and debris, as well as from impact damage and the like.
In other embodiments, the grade predetermination function of the microprocessor may be replaced by a mechanical grade indicator, such as a string, line or surface, and the microprocessor voltage or signal generation function may be replaced mechanically, such as by a contact switch or control armature or member.
In one embodiment, as shown in FIG. 13 , a kit 250 is provided for retrofitting existing buckets. The kit 250 includes an interrupt bar 55 operationally connected to a piston actuator 45 and connectable to and/or slidingly disposed in a housing 210 . The housing 210 is structurally connectable to a bucket, such as by bolting, welding, or the like, to define a bottom wall 210 . One or more s sensors 15 , 20 are typically connected to, and more typically disposed within, the housing 210 and are likewise operationally connectable to a controller 25 (as shown in previous FIGs.). The piston actuator 45 is connectable to a hydraulic pressure source.
In another embodiment, as shown in FIGS. 14A and 14B , a system 310 is shown wherein hydraulic cylinders 345 are connected to a bucket 350 and may be energized to pivot an interrupt plate 355 pivotably connected thereto, urging the plate 355 into engagement with the ground to maintain controlled contact of the bucket 350 with the ground and ensure a maximum depth of cut. The cylinders 345 are illustrated as positioned in the exterior top portion of the bucket 350 . The bucket 350 is illustrated as a wide bucket having an aspect ratio similar to that of a loader or dozer bucket or blade, but may have any convenient shape.
While the novel technology has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character. It is understood that the embodiments have been shown and described in the foregoing specification in satisfaction of the best mode and enablement requirements. It is understood that one of ordinary skill in the art could readily make a nigh-infinite number of insubstantial changes and modifications to the above-described embodiments and that it would be impractical to attempt to describe all such embodiment variations in the present specification. Accordingly, it is understood that all changes and modifications that come within the spirit of the novel technology are desired to be protected.
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A kit for modifying a digging bucket for controlling the depth cut, including an elongated member operationally connectable to a hoe bucket defining a cutting edge, an actuator operationally connectable to the elongated member, an electronic controller operationally connectable to the actuator, and a position sensor operationally connectable to the cutting edge and operationally connectable to the electronic controller. The actuator may be energized to pivot the elongated member to a position adjacent the cutting edge for engaging ground. Positioning of the elongated member adjacent the cutting edge prevents the cutting edge from digging ground.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This patent arises from a continuation of U.S. patent application Ser. No. 14/319,326, filed Jun. 30, 2014. U.S. patent application Ser. No. 14/319,326 is hereby incorporated herein by reference in its entirety.
FIELD OF THE DISCLOSURE
[0002] This disclosure relates generally to virtual machine computing and, more particularly, to methods and apparatus to manage monitoring agents in a virtual machine computing cloud.
BACKGROUND
[0003] “Infrastructure-as-a-Service” (also commonly referred to as “IaaS”) generally describes a suite of technologies provided by a service provider as an integrated solution to allow for elastic creation of a virtualized, networked, and pooled computing platform (sometimes referred to as a “cloud computing platform”). Enterprises may use IaaS as a business-internal organizational cloud computing platform (sometimes referred to as a “private cloud”) that gives an application developer access to infrastructure resources, such as virtualized servers, storage, and networking resources. By providing ready access to the hardware resources required to run an application, the cloud computing platform enables developers to build, deploy, and manage the lifecycle of a web application (or any other type of networked application) at a greater scale and at a faster pace than before.
[0004] Deployment tools currently in use are usually a patchwork of various software products from different vendors and/or homegrown solutions. Such tools are generally process-driven with heavy reliance on custom scripts and property files. Traditional deployment tools are also not configured for automation with cloud computing platforms that dynamically provision virtual computing resources.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 is a block diagram of an example system constructed in accordance with the teachings of this disclosure for automatically managing monitoring agents.
[0006] FIG. 2 is a block diagram of an example virtual machine that may be analyzed by the example system of FIG. 1 to determine whether to install and/or remove a monitoring agent to monitor the virtual machine.
[0007] FIG. 3 illustrates an example interface that may be presented by the service rule definer of FIG. 1 to facilitate creation and/or management of a service rule.
[0008] FIG. 4 is a flowchart representative of example machine readable instructions that may be executed to implement the system of FIG. 1 to automatically install a monitoring agent on a computing unit.
[0009] FIG. 5 is a flowchart representative of example machine readable instructions that may be executed to implement the system of FIG. 1 to automatically install monitoring agents on computing units based on a multi-tiered application.
[0010] FIG. 6 is a flowchart representative of example machine readable instructions that may be executed to implement the system of FIG. 1 to automatically remove and/or reconfigure a monitoring agent when a service is removed from a computing unit.
[0011] FIG. 7 is a block diagram of an example processor platform capable of executing the instructions of FIGS. 4, 5 , and/or 6 to implement the system of FIG. 1 .
[0012] Wherever possible, the same reference numbers will be used throughout the drawing(s) and accompanying written description to refer to the same or like parts.
DETAILED DESCRIPTION
[0013] Monitoring agents are installed on computing units (e.g., virtual machines (VM), physical machines (PM), etc.) to, for example, monitor the performance of applications. Because monitoring agents are resource intensive, virtual infrastructure administrators typically install monitoring agents on computing units running important services (e.g., web servers, application servers, database servers, application components, etc.) that need to be monitored (and typically do not install monitoring agents on other less important computing units). Currently, the virtual infrastructure administrators manually install and configure monitoring agents on the computing units with services to be monitored. Because virtual environments are dynamic, applications (e.g., multi-tiered applications) and services may be scaled out automatically (e.g., by adding additional resources, services, applications, etc.). The automatic scaling of the applications and the services may require the installation of new monitoring agent(s) across new computing units and/or may require existing monitoring agents to be reconfigured for the new services and/or applications. Additionally, as services and/or applications are moved and/or removed, monitoring agents may require reconfiguration or removal from a computing unit.
[0014] To accommodate management of monitoring agents (e.g., without user intervention), in examples disclosed herein, a user (e.g., the virtual infrastructure administrator) defines service rules. The service rules may, for example, define the service(s) that require monitoring agents, the computing units and/or groups to monitor for the service(s), and/or criteria for installation (e.g., install/configure a monitoring agent for every detected instance of a service, install a monitoring agent only when a service is newly installed, etc.). The service rule may also define configuration information (e.g., IP address, installation source, credentials, etc.) relating to a monitoring agent server, service metrics to be reported to the monitoring agent server, and/or configuration properties for the monitoring agent server.
[0015] A virtual infrastructure navigator (VIN), as disclosed herein, may automatically discover services executing on computing units specified by the service rules. Example systems for automatically discovering services are discussed in U.S. application Ser. No. 14/231,018 entitled “Methods and Apparatus to Automatically Configure Monitoring of a Virtual Machine,” which is incorporated by reference herein in its entirety. If a discovered service satisfies a service rule (e.g., matches the defined application and/or service, is running on a specified computing unit, and meets the specified criteria), an agent installer installs a monitoring agent on a target computing unit and/or configures the monitoring agent according to the service rule.
[0016] In some examples disclosed herein, the VIN causes discovery scripts to be executed by the computing units. In some such examples, the VIN detects changes in the configuration (e.g., detects that a service has been installed, detects that a service has been removed, etc.) of the computing units. In some such examples, automatically installing a monitoring agent on a computing unit is triggered by the VIN detecting changes in the configuration of the computing unit.
[0017] In some examples disclosed herein, the VIN automatically discovers the installation of multi-tiered applications. In some such examples, the VIN identifies services installed as part of the multi-tiered applications, identifies computing units corresponding to the services, and installs and/or configures monitoring agents on computing units with services that satisfy one or more service rules.
[0018] In some examples disclosed herein, the VIN automatically detects when a service has been removed from a computing unit. The example VIN determines whether, according to a service rule, a monitoring agent was installed and/or configured for the service on the computing unit. In some such examples, without user intervention, the monitoring agent is reconfigured so that the monitoring agent does not attempt to monitor the removed service. Additionally or alternatively, the monitoring agent is removed from the computing unit. In this manner, unnecessary monitoring agents are removed from the deployment environment and resources are freed.
[0019] Example methods and apparatus disclosed herein facilitate the automatic management of monitoring agents deployed in a deployment environment. Example methods and apparatus enable a user (e.g., a virtual infrastructure administrator, etc.) to define service rules for services and/or applications that are monitored. In some example methods and apparatus, a VIN (e.g., vCenter™ Infrastructure Navigator™, a commercially available product from VMWare®, Inc.) or similar component automatically detects services running on a computing unit (e.g., a virtual machine, a physical machine, etc.). In some examples, the automatically detected services are compared to the defined service rules. If an automatically detected service satisfies a service rule (e.g., the automatically detected service is identified in the service rule), a monitoring agent is installed and/or configured on the computing unit running the service without further intervention from the user.
[0020] Example methods disclosed herein include determining if a first service is installed on computing unit (e.g., a virtual machine, a physical machine, etc.) that corresponds to a service rule, the service rule to specify a service identifier and configuration for a monitoring agent, determining if the virtual machine includes the monitoring agent, and in response to determining that the first service matches the service identifier and determining that the monitoring agent is not installed on the virtual machine, initiating installation of the monitoring agent on the virtual machine.
[0021] Example apparatus disclosed herein include a service analyzer to determine whether if a virtual machine has a first service installed that corresponds to a service rule and to determine if the virtual machine has a monitoring agent corresponding to the first service, the service rule to specify a service identifier and a configuration for the monitoring agent, and an agent installer to, in response to the first service matching the service identified specified by the service rule and the monitoring agent not installed on the virtual machine, initiate installation of the monitoring agent on the virtual machine.
[0022] As used herein, the term “node” or “logical node” refers to a computing unit or a cluster of computing units defined in a service rule to be monitored for a specified service.
[0023] As used herein, the term “service” refers to scripted software that can be installed on a computing unit and may be reused in multiple applications.
[0024] As used herein, the term “properties” refers to configuration variables used by scripts to set parameters on a script and run various configurations. For example, setting an installation path property value causes installation scripts to use the property to specify the path to use to install a monitoring agent.
[0025] As used herein, the term “deployment environment” refers to a computing environment in a cloud provider. For example, separate deployment environments may be used for development, testing, staging, and/or production. A cloud provider can have one or multiple deployment environments.
[0026] FIG. 1 illustrates an example system 100 for automatically managing monitoring agents 102 deployed across computing units 104 (e.g., virtual machines (VM), physical machines (PM), etc.) managed by a cloud platform provider 106 (also referred to herein as a “cloud provider”). The example system 100 includes a monitoring agent server 110 and a virtual infrastructure navigator (VIN) 112 , which may be used to automatically deploy, configure, and/or remove monitoring agents 102 . The system 100 of the illustrated example includes a discovery script repository 126 in communication with the VIN 112 .
[0027] The example cloud computing platform provider 106 provisions virtual and/or physical computing resources (e.g., the computing units 104 ) to provide the deployment environments 108 in which the administrator 114 and/or developer 116 can deploy multi-tiered application(s). One particular example of a deployment environment that may be used to implement the deployment environments 112 of FIG. 1 is vCloud DataCenter cloud computing services available from VMWare®, Inc. The example cloud computing platform provider 106 of FIG. 1 may be used to provide multiple deployment environments 108 , for example, for development, testing, staging, and/or production of applications. The administrator 114 and/or the developer 116 may access services from the cloud computing platform provider 106 , for example, via REST (Representational State Transfer) APIs (Application Programming Interface) and/or via any other client-server communication protocol. One particular implementation of a REST API for cloud computing services is vCloud® Director API available from VMWare®, Inc.
[0028] In the example illustrated in FIG. 1 , the example deployment environment 108 includes multiple computing units 104 (e.g., virtual machines (VM) and physical machines (PM)). In the illustrated example of FIG. 1 , services 117 (e.g., MySql server, e-mail server, etc.) are deployed across the example computing units 104 in the deployment environment 108 . In some examples, computing units 104 are added and/or removed from the deployment environment 108 by the administrator 114 and/or the developer 116 . During the use of a multi-tiered application (e.g., an application with multiple services 117 spread across one or more computing units 104 ), the multi-tiered application may be dynamically scaled up (e.g., by adding services 117 and/or computing units 104 associated with the application) or scaled down (e.g., by removing services 117 and/or computing units 104 associated with the application) to add or remove resources as required by the multi-tiered applications.
[0029] In the example illustrated in FIG. 1 , the VIN 112 includes a service analyzer 118 , a service rule definer 120 , an agent installer 122 , and a service rule database 124 . The example service rule database 124 is provided to store and/or manage service rules created, deleted, and/or modified by the example service rule definer 120 .
[0030] In the example illustrated in FIG. 1 , the administrator 114 and/or the developer 116 use the service rule definer 120 to maintain the service rule database 124 by creating, modifying, and/or deleting service rules. In the illustrated example, the service rule database 124 stores the service rules generated via the service rule definer 120 . In some examples, the service rule database 124 may be any data structure suitable for storing data, such as a relational database (e.g., a MySQL database), or an Extensible Markup Language (XML) file, etc. The example service rule definer 120 is to create, delete, and/or modify service rules used by the example service analyzer 118 to determine whether an example monitoring agent 102 is to be installed, removed, and/or configured on an example computing unit 104 . Additionally or alternatively, service rules may be imported into the service rule database 124 and may be subsequently maintained by the service rule definer 120 .
[0031] In the example illustrated in FIG. 1 , the service analyzer 118 is to monitor services deployed on computing units 104 in the example deployment environment 108 , to determine whether an example monitoring agent 102 is to be installed, removed, and/or configured on an example computing unit 104 . The example service analyzer 118 may additionally or alternatively direct the example agent installer 122 to install, remove, and/or configure an example monitoring agent 102 on an example computing unit 104 . The example service analyzer 118 selects and/or accesses discovery script(s) stored in the example discovery script repository 126 . In some examples, the discovery script repository 126 may be any data structure suitable for storing data, such as a relational database (e.g., a MySQL database), or an Extensible Markup Language (XML) file, etc. In some examples, the discovery scripts are sets of instructions to be executed by computing units 104 analyzer and/or report the configuration of the computing unit 104 . The service analyzer 118 of the illustrated example causes the discovery script(s) to be executed on the computing units 104 in the deployment environment 108 to detect changes in the configuration (e.g., detects installation of new services, detects removal of services, etc.) of the computing units 104 in the deployment environment 108 . Additionally or alternatively, the computing units 104 , from time to time, report the services installed on the computing units 104 to the VIN 112 and/or the service analyzer 118 .
[0032] The example service analyzer 118 compares the service(s) 117 running on the example computing units 104 to the service rules in the service rule database 124 . If a service satisfies a service rule (e.g., meets the criteria defined in the service rule), the example service analyzer 118 directs the example agent installer 112 to initiate installation and/or configuration of an example monitoring agent 102 on example the computing unit 104 corresponding to the service. For example, a service 117 may satisfy a service rule when the service matches a service identifier included in the service rule. In some examples, the service analyzer 118 also detects when services have been removed from the computing units 104 . In some such examples, the example service analyzer 118 directs the example agent installer 122 to initiate removal of the example monitoring agent 102 from the corresponding example computing unit 104 (e.g., when no other service is being monitored by the example monitoring agent 102 ) and/or to reconfigure the example monitoring agent 102 (e.g., when another service is being monitored by the example monitoring agent 102 ). In some examples, the service analyzer 118 does not respond to detecting that a service 117 has been removed from a computing unit 104 (e.g., does not remove the example monitoring agent).
[0033] In the example illustrated in FIG. 1 , the agent installer 122 initiates installation, configuration and/or removal of a monitoring agent 102 from the computing unit 104 when directed by the service analyzer 112 according to a service rule. The example service rule identifies an initial configuration of the example monitoring agent 102 installed on the example target computing unit 104 . In some examples, the service rule defines a configuration for the agent server 110 . An example configuration includes an internet protocol (IP) address of the monitoring agent server 110 , an agent user name, an agent user password, an installation package location, a Linux platform installation directory, a Windows platform installation directory, an agent version, configuration of the agent 102 as a service, a secure connection configuration to the monitoring agent server 110 , a performance agent server port, a performance agent secure server port, a performance agent port, a unidirectional configuration (e.g., configuring either the monitoring agent 102 or the monitoring agent server 110 to initiate all communications, or configuring the monitoring agent 102 and the monitoring agent server 110 to initiate respective communications), and/or a checksum hash value. In some examples, the example service rule defines which metrics supported by the example monitoring agent 102 are to be monitored and reported to the example monitoring agent server 110 .
[0034] After the example agent installer 122 of FIG. 1 causes the installation and/or configuration of the monitoring agents 102 on the appropriate computing units 104 , the example monitoring agent server 110 of FIG. 1 automatically registers the monitoring agents 102 on the computing units 104 (e.g., based on how the monitoring agents 102 are configured to communicate with the example monitoring agent server 110 ). Additionally, example agent installer 122 configures the computing units 104 to be monitored according to a management or monitoring policy and/or performs any other monitoring tasks associated with the service. For example, the computing units 104 may be configured to allow the monitoring agent 102 to communicate with the monitoring agent server 110 (e.g., configure permissions on the computing unit 104 , configure firewall of the computing unit 104 , etc.).
[0035] In some examples, the example monitoring agent server 110 of FIG. 1 automatically organizes the monitoring of the services. For example, the monitoring agent server 110 may group monitoring of the services 117 to enable ease of access by the administrator 114 and/or the developer 116 . In some examples, the monitoring agent server 110 may group the services 117 installed on the example computing units 104 of FIG. 1 for access by the administrator 114 in association with a multi-tiered application. In some examples, the monitoring agent server 110 may group monitoring agents 102 on the example computing units 104 that are associated with email server services. In such an example, the administrator 116 may then access or view performance information monitored by the monitoring agents 102 for the email servers by selecting an email server group in a monitoring agent management interface (e.g., vCenter™ Hyperic® available from VMWare®, Inc.). In some examples, the monitoring agent management interface may be accessed via the monitoring agent server 110 .
[0036] FIG. 2 is a block diagram of an example implementation of a virtual machine (VM) 200 executing within the development environment 108 of FIG. 1 . The example VM 200 is one of the computing units 104 that is virtualized on physical resources 202 (e.g., processor(s), memory, storage, peripheral devices, network access, etc.) provided by the example development environment 108 . In the illustrated example the physical resources 202 are managed by a virtual machine manager (VMM) 204 of FIG. 2 . In the illustrated example, the VMM 204 creates virtualized hardware 206 (e.g., virtualized storage, virtualized memory, virtualized processor(s), etc.) to allow multiple VMs 200 to be instantiated in the deployment environment 108 using the same physical resources 202 . In some examples, the VMM 204 manages the physical resources 202 (e.g., creates the virtualized hardware 206 ) based on polices implemented by the administrator 114 ( FIG. 1 ) and/or the developer 116 ( FIG. 1 ). For example, a policy may restrict access to particular locations in memory and/or storage, etc.
[0037] In some examples, the VIN 112 of FIG. 1 is provided with credentials (e.g., a user name and password of a user or administrator authorized to access the relevant portions of the VM 200 ) to access the components and/or properties of the VM 200 via communications interface 208 of the VMM 204 and/or a communications interface 210 . In some examples, the VIN 112 may issue text-based commands to the VM 200 to initiate discovery scripts and/or initiate installation of the monitoring agent 102 . In some examples, the VMM 204 and/or the VM 200 may report information about the services installed on the VM 200 to the VIN 112 .
[0038] In the example illustrated in FIG. 2 , the VM 200 executes a guest operating system (OS) 212 (e.g., a Windows operating system, a Linux operating system, etc.). In the illustrated example, the guest OS 212 executes the services 117 . Alternatively, the services 117 may be executed in a different environment of the VM 200 (e.g., the services 117 may execute natively on the VM 200 , etc.). Additionally, the example guest OS 212 executes the example monitoring agent 102 ( FIG. 1 ) installed by the agent installer 122 ( FIG. 1 ) based on the service rules to monitor services installed on the VM 200 . Alternatively, the monitoring agent 102 may be executed in a different environment of the VM 200 (e.g., the monitoring agent 102 may execute natively on the VM 200 , the monitoring agent 102 may execute on the physical resources, etc.).
[0039] While an example manner of implementing the system 100 is illustrated in FIGS. 1 and/or 2 , one or more of the elements, processes and/or devices illustrated in FIGS. 1 and/or 2 may be combined, divided, re-arranged, omitted, eliminated and/or implemented in any other way. Further, the example monitoring agents 102 , the example computing units 104 , the example development environment 108 , the example monitoring agent server 110 , the example virtual infrastructure navigator 112 , the example service analyzer 118 , the example service rule definer 120 , the example agent installer 122 , the example service rule database 124 , the example VM 200 , and/or, more generally, the example system 100 of FIG. 1 may be implemented by hardware, software, firmware and/or any combination of hardware, software and/or firmware. Thus, for example, any of the example monitoring agents 102 , the example computing units 104 , the example development environment 108 , the example monitoring agent server 110 , the example virtual infrastructure navigator 112 , the example service analyzer 118 , the example service rule definer 120 , the example agent installer 122 , the example service rule database 124 , the example VM 200 , and/or, more generally, the example system 100 of FIG. 1 could be implemented by one or more analog or digital circuit(s), logic circuits, programmable processor(s), application specific integrated circuit(s) (ASIC(s)), programmable logic device(s) (PLD(s)) and/or field programmable logic device(s) (FPLD(s)). When reading any of the apparatus or system claims of this patent to cover a purely software and/or firmware implementation, at least one of the example monitoring agents 102 , the example computing units 104 , the example development environment 108 , the example monitoring agent server 110 , the example virtual infrastructure navigator 112 , the example service analyzer 118 , the example service rule definer 120 , the example agent installer 122 , the example VM 200 , and/or the example service rule database 124 is/are hereby expressly defined to include a tangible computer readable storage device or storage disk such as a memory, a digital versatile disk (DVD), a compact disk (CD), a Blu-ray disk, etc. storing the software and/or firmware. Further still, the example system 100 of FIGS. 1 and/or 2 may include one or more elements, processes and/or devices in addition to, or instead of, those illustrated in FIGS. 1 and/or 2 , and/or may include more than one of any or all of the illustrated elements, processes and devices.
[0040] FIG. 3 illustrates an example interface 300 that may be presented by the example service rule definer 120 of FIG. 1 (e.g., to the administrator 114 and/or the developer 116 of FIG. 1 ) to enable creation and/or management of a service rule. Example configuration information includes a service rule name 302 , an identifier 304 of application(s) and/or service(s) to be monitored, nodes 306 to monitor for the application(s) and/or the service(s) (e.g., the application(s) and/or service(s) identified by identifier 304 ), group(s) 308 to monitor for the application(s) and/or the service(s) to be monitored, criteria 310 , agent server configuration information 312 (e.g., agent server address, agent server credentials, etc.), metrics to be monitored 314 , and/or configuration properties 316 . The example configuration information 302 - 316 may be configured by the example administrator 114 and/or the example developer 116 .
[0041] The example service rule name 302 is provided to facilitate the example administrator 114 and/or the example developer 116 to assign a name to the example service rule (e.g., in accordance with cloud provider administration policies). The identifier 304 is provided to enable the example administrator 114 and/or the example developer 116 to define one or more applications and/or services to be monitored. For example, a service rule may be defined for one or more services 117 , such as, MySQL 5.x servers and MySQL 4.x servers. For example, a service rule may be defined for a multi-tiered application, such as, Exchange 2010 (e.g., including agent server configuration information 312 , metrics to be monitored 314 , and/or configuration properties 316 for the services related to Exchange 2010). In the illustrated example, a node field 306 and/or a group field 308 are provided to display a selection of nodes and/or groups to define the computing units (e.g., the computing units 104 of FIG. 1 ) to monitor for the application(s) and/or service(s) to be monitored (e.g., as identified by identifier 304 ). In some examples, the node field 306 and/or the group field 308 may be left blank and/or may not be provided on the interface 300 (e.g., any computing unit 104 in the development environment 108 and/or the cloud provider 106 ( FIG. 1 ) may be monitored for the application(s) and/or service(s) to be monitored). An example criteria field 310 may be provided to allow criteria to be specified (e.g., though text input, through selection of items on a list, etc.) For example, criteria specified in the criteria field 310 may define conditions that will cause the example service analyzer 118 of FIG. 1 to signal the example agent installer 122 of FIG. 1 to initiate installation, configuration and/or removal of an example monitoring agent 102 . For example, criteria may be selected in the criteria field 310 so that monitoring agents 102 are installed only in response to detecting newly installed services (e.g., services 117 of FIG. 1 ) (as opposed to services 117 currently installed on a computing unit 104 at the time the service rule is created). In some examples, the criteria field 310 may be left blank or may not be included interface 300 (e.g., no additional criteria is required to initiate installation and/or configuration of a monitoring agent).
[0042] One or more agent server configuration information fields 312 are provided to allow the example administrator 114 and/or the example developer 116 to define configuration information (e.g., an IP address of the example monitoring agent server 110 of FIG. 1 , an agent user name, an agent user password, an installation package location, a Linux platform installation directory, a Windows platform installation directory, an agent version, configuration of the example agent 102 as a service, a secure connection configuration to the example monitoring agent server 110 , a performance agent server port, a performance agent secure server port, a performance agent port, a unidirectional configuration, and/or a checksum hash value, etc.) to install and/or configure a monitoring agent 102 (e.g., to allow the automatically installed example monitoring agent 102 to communicate with the example monitoring agent server 110 of FIG. 1 ). In the illustrated example, one or more example metric fields 312 are provides to allow the administrator 114 and/or the developer 116 to define information to be monitored by the monitoring. In some examples, the selectable metrics in the metrics field 314 are defined according to specific services and/or applications (e.g., the services and/or the application indicated by the example identifier 304 ). In some examples, the administrator 114 and/or the developer 116 select one or more of the metrics 314 to be monitored and select an interval (e.g., 5 minutes, default interval defined for the metric, etc.). In the illustrated example, one or more properties 316 are provided to receive a property selection. In some examples, the available property selection is determined by the identifier 304 . The example properties 316 specify parameters the example agent installer 122 uses to configure the example monitoring agent 102 according to the preferences of the administrator 114 and/or the developer 116 .
[0043] Flowchart representative of example machine readable instructions for implementing the example VIN 112 , the example monitoring agent server 110 and/or the example discovery script repository 126 of FIG. 1 are shown in FIGS. 4, 5 , and/or 6 . In these examples, the machine readable instructions comprise a program for execution by a processor such as the processor 712 shown in the example processor platform 700 discussed below in connection with FIG. 7 . The program may be embodied in software stored on a tangible computer readable storage medium such as a CD-ROM, a floppy disk, a hard drive, a digital versatile disk (DVD), a Blu-ray disk, or a memory associated with the processor 712 , but the entire program and/or parts thereof could alternatively be executed by a device other than the processor 712 and/or embodied in firmware or dedicated hardware. Further, although the example programs are described with reference to the flowcharts illustrated in FIGS. 4, 5, and 6 , many other methods of implementing the example VIN 112 , the example monitoring agent server 110 and/or the example discovery script repository 126 may alternatively be used. For example, the order of execution of the blocks may be changed, and/or some of the blocks described may be changed, eliminated, or combined.
[0044] As mentioned above, the example processes of FIGS. 4, 5 , and/or 6 may be implemented using coded instructions (e.g., computer and/or machine readable instructions) stored on a tangible computer readable storage medium such as a hard disk drive, a flash memory, a read-only memory (ROM), a compact disk (CD), a digital versatile disk (DVD), a cache, a random-access memory (RAM) and/or any other storage device or storage disk in which information is stored for any duration (e.g., for extended time periods, permanently, for brief instances, for temporarily buffering, and/or for caching of the information). As used herein, the term tangible computer readable storage medium is expressly defined to include any type of computer readable storage device and/or storage disk and to exclude propagating signals and to exclude transmission media. As used herein, “tangible computer readable storage medium” and “tangible machine readable storage medium” are used interchangeably. Additionally or alternatively, the example processes of FIGS. 4, 5 , and/or 6 may be implemented using coded instructions (e.g., computer and/or machine readable instructions) stored on a non-transitory computer and/or machine readable medium such as a hard disk drive, a flash memory, a read-only memory, a compact disk, a digital versatile disk, a cache, a random-access memory and/or any other storage device or storage disk in which information is stored for any duration (e.g., for extended time periods, permanently, for brief instances, for temporarily buffering, and/or for caching of the information). As used herein, the term non-transitory computer readable medium is expressly defined to include any type of computer readable storage device and/or storage disk and to exclude propagating signals and to exclude transmission media. As used herein, when the phrase “at least” is used as the transition term in a preamble of a claim, it is open-ended in the same manner as the term “comprising” is open ended.
[0045] FIG. 4 is a flowchart representative of example machine readable instructions 400 which may be executed to implement the system 100 of FIG. 1 to automatically install a monitoring agent (e.g., the example monitoring agent 102 of FIGS. 1 and 2 ) on a computing unit (e.g., the example computing unit 104 of FIG. 1 and/or the example VM 200 of FIG. 2 ). Initially, at block 402 , the service rule definer 120 ( FIG. 1 ) defines a service rule. In some examples, the example service rule definer 120 defines a service rule after receiving input from the administrator 114 ( FIG. 1 ) and/or the developer 116 ( FIG. 1 ) via the example interface 300 ( FIG. 3 ). At block 404 , the example service analyzer 118 ( FIG. 1 ) automatically detects a service (e.g., the example service 117 of FIG. 1 ) installed on a computing unit 104 . At block 406 , the example service analyzer 118 determines whether the example service 117 detected at block 404 satisfies the example service rule defined at block 402 . In some examples, the service 117 satisfies the service rule if the service corresponds to an identifier of service(s) to be monitored (e.g. the identifier 304 of FIG. 3 ) defined in the service rule. Additionally or alternatively, the service 117 say satisfy the service rule if the computing unit 104 on which the service 117 is installed corresponds to a computing unit 104 specified by nodes and/or groups (e.g., specified by the example node field 306 and/or the example group field 308 of FIG. 3 ) defined in the service rule. Additionally or alternatively, the service 117 may satisfy the service rule if the criteria (e.g., the criteria specified in the criteria field 310 of FIG. 3 ) defined by the service rule is met (e.g., the service 117 is newly installed on the computing unit 104 , etc.). If the service 117 satisfies the service rule, program control advances to block 408 . Otherwise, if the service 117 does not satisfy the service rule, program control returns to block 404 .
[0046] At block 408 , the example service analyzer 118 determines whether a monitoring agent (e.g., the example monitoring agent 102 of FIG. 1 ) is installed on the computing unit 104 corresponding to the service 117 detected at block 404 . If a monitoring agent 102 is not installed on the computing unit 104 , program control advances to block 410 . Otherwise, program control advances to block 412 . At block 410 , the example agent installer 122 ( FIG. 1 ) initiates installation of the example monitoring agent 102 on the computing unit 104 corresponding to the service 117 detected at block 404 . In some examples, the agent installed 122 initiates the installation of the monitoring agent 102 without intervention from a user (e.g., the administrator 114 or the developer 116 , etc.). Program control then advances to block 412 . At block 412 , the agent installer 122 configures the monitoring agent 102 according to the configuration information 312 - 316 ( FIG. 3 ) defined in the service rule defined at block 402 . In some examples, the agent installer 122 configures the monitoring agent 102 without intervention from a user. Example program 400 then ends.
[0047] FIG. 5 is a flowchart representative of example machine readable instructions 500 that may be executed to implement the example system 100 of FIG. 1 to automatically (e.g., without user intervention) install monitoring agents (e.g., a monitoring agent 102 of FIG. 1 ) on a computing unit (e.g., the example computing unit 104 of FIG. 1 ) in response to detecting installation of a multi-tiered application. Initially, at block 502 , the example service rule definer 120 ( FIG. 1 ) defines a service rule. In some examples, the service rule definer 120 defines a service rule after receiving input from the administrator 114 ( FIG. 1 ) and/or the developer 116 ( FIG. 1 ) (e.g., through the interface 300 of FIG. 3 ). At block 504 , the example service analyzer 118 ( FIG. 1 ) automatically (e.g., without user intervention) detects installation of a multi-tiered application on the computing unit 104 within a deployment environment (e.g., the example deployment environment 108 of FIG. 1 ).
[0048] At block 506 , the example service analyzer 118 ( FIG. 1 ) determines whether the multi-tiered application satisfies a service rule. In some examples, the multi-tiered application satisfies the service rule if the multi-tiered application corresponds to an identifier of multi-tiered application(s) to be monitored (e.g. the identifier 304 of FIG. 3 ) defined in the service rule. Additionally or alternatively, the multi-tiered application satisfies the service rule if the computing units 104 corresponding to the multi-tiered application is installed on corresponds to a computing units 104 specified by nodes and/or groups (e.g., as specified by the node field 306 and/or the group field 308 of FIG. 3 ) defined in the service rule. Additionally or alternatively, the multi-tiered application satisfies the service rule if the criteria (e.g., the criteria specified by the criteria field 310 of FIG. 3 ) defined by the service rule is met (e.g., the multi-tiered application is newly installed on the computing unit 104 , etc.). If a service rule is satisfied, program control advances to block 508 . Otherwise, if a service rule is not satisfied, program control returns to block 504 .
[0049] At block 508 , the service analyzer 118 detects services(s) and corresponding computing units 104 related to the installation of the multi-tiered application. In some examples, the service analyzer 118 receives an application definition (e.g., a list of the example services 117 and the example computing units 104 on which those services 117 were installed, etc.). In some examples, the service analyzer 118 causes example discovery scripts (e.g., the discovery scripts stored in the discovery script repository 126 of FIG. 1 ) to be executed on the computing units 104 in the example deployment environment 108 to discover relationships between the services 117 related to the multi-tiered application and the computing units 104 on which the services 117 are installed. At block 510 , the service analyzer 118 selects the computing unit 104 detected at block 508 .
[0050] At block 512 , the service analyzer 118 determines whether a monitoring agent (e.g., the example monitoring agent 102 of FIGS. 1 and/or 2 ) is installed on the computing unit 104 selected at block 510 . If the monitoring agent 102 is not installed on the computing device 104 , program control advances to block 514 . Otherwise, if the monitoring agent 102 is installed on the computing device 104 , program control advances to block 516 .
[0051] At block 514 , without intervention from a user (e.g., the administrator 114 or the developer 116 , etc.), the agent installer 122 ( FIG. 1 ) initiates installation of the monitoring agent 102 on the computing unit 104 selected at block 510 . Program control then advances to block 516 .
[0052] At block 516 , without intervention from a user (e.g., the administrator 114 or the developer 116 , etc.), the agent installer 122 configures the monitoring agent 102 according to the configuration information 312 - 316 ( FIG. 3 ) defined in the service rule defined at block 502 . At block 518 , the service analyzer 118 determines whether there is another one of the computing units 104 detected at block 508 that requires the monitoring agent 102 to be installed and/or configured. If there is another one of the computing units 104 , program control returns to block 510 . Otherwise, the example program 500 ends.
[0053] FIG. 6 is a flowchart representative of example machine readable instructions 600 which may be executed to implement the example system 100 of FIG. 1 to automatically (e.g., without user intervention) remove and/or reconfigure a monitoring agent (e.g., the example monitoring agent 102 of FIGS. 1 and 2 ) when a service (e.g., the example service 117 of FIG. 1 ) is removed from a computing unit (e.g., the example computing unit 104 of FIG. 1 ). Initially, at block 602 , the example service analyzer 118 ( FIG. 1 ) automatically detects the removal of the service 117 from the computing device 104 . At block 604 , the service analyzer 118 determines whether the service 117 detected at block 602 satisfies a service rule. In some examples, the service 117 satisfies the service rule if the service corresponds to an identifier of a service to be monitored (e.g. the identifier 304 of FIG. 3 ) defined in the service rule. Additionally or alternatively, the service 117 satisfies the service rule if the computing unit 104 on which the service 117 was installed corresponds to the computing unit 104 specified by nodes and/or groups (e.g., the nodes 306 and/or the groups 308 of FIG. 3 ) defined in the service rule. Additionally or alternatively, the service 117 satisfies the service rule if the criteria (e.g., the criteria specified by the criteria field 310 of FIG. 3 ) defined by the service rule is met (e.g., the service rule allows for removal of a monitoring agent 102 , etc.). If the service 117 satisfies the service rule, program control advances to block 606 . Otherwise, if the service 117 does not satisfy the service rule, program control returns to block 602 .
[0054] At block 606 , the service analyzer 118 determines whether the monitoring agent 102 installed on the computing unit 104 detected at block 602 is monitoring another service. If the monitoring agent 102 is monitoring another service, then program control advances to block 608 . Otherwise, if the monitoring agent 102 is not monitoring another service, program control advances to block 610 .
[0055] At block 608 , the agent installer 122 ( FIG. 1 ) initiates reconfiguration of the monitoring agent 102 to remove configuration information (e.g., the configuration information 312 - 316 ) related to the removed service 102 according to the service rule. In some examples, the agent installer 122 initiates the reconfiguration of the monitoring agent 102 without intervention from a user (e.g., an administrator 114 and/or a developer 116 of FIG. 1 , etc.). The example program 600 of FIG. 6 then ends.
[0056] At block 610 , the agent installer 122 initiates removal of the monitoring agent 102 from the computing unit 104 detected at block 602 . In some examples, the agent installer 122 initiates removal of the monitoring agent without intervention from the user. The example program 600 of FIG. 6 then ends.
[0057] FIG. 7 is a block diagram of an example processor platform 800 capable of executing the instructions of FIGS. 4, 5 , and/or 6 to implement the example system 100 of FIG. 1 . The processor platform 700 can be, for example, a server, a personal computer, or any other type of computing device.
[0058] The processor platform 700 of the illustrated example includes a processor 712 . The processor 712 of the illustrated example is hardware. For example, the processor 712 can be implemented by one or more integrated circuits, logic circuits, microprocessors or controllers from any desired family or manufacturer.
[0059] The processor 712 of the illustrated example includes a local memory 713 (e.g., a cache). The processor 712 of the illustrated example is in communication with a main memory including a volatile memory 714 and a non-volatile memory 716 via a bus 718 . The volatile memory 714 may be implemented by Synchronous Dynamic Random Access Memory (SDRAM), Dynamic Random Access Memory (DRAM), RAMBUS Dynamic Random Access Memory (RDRAM) and/or any other type of random access memory device. The non-volatile memory 716 may be implemented by flash memory and/or any other desired type of memory device. Access to the main memory 714 , 716 is controlled by a memory controller.
[0060] The processor platform 700 of the illustrated example also includes an interface circuit 720 . The interface circuit 720 may be implemented by any type of interface standard, such as an Ethernet interface, a universal serial bus (USB), and/or a PCI express interface.
[0061] In the illustrated example, one or more input devices 722 are connected to the interface circuit 720 . The input device(s) 722 permit(s) a user to enter data and commands into the processor 812 . The input device(s) can be implemented by, for example, a keyboard, a button, a mouse, a touchscreen, a track-pad, a trackball, isopoint and/or a voice recognition system.
[0062] One or more output devices 724 are also connected to the interface circuit 720 of the illustrated example. The output devices 724 can be implemented, for example, by display devices (e.g., a light emitting diode (LED), an organic light emitting diode (OLED), a liquid crystal display, a cathode ray tube display (CRT), a touchscreen, a tactile output device, a printer and/or speakers). The interface circuit 720 of the illustrated example, thus, typically includes a graphics driver card, a graphics driver chip or a graphics driver processor.
[0063] The interface circuit 720 of the illustrated example also includes a communication device such as a transmitter, a receiver, a transceiver, a modem and/or network interface card to facilitate exchange of data with external machines (e.g., computing devices of any kind) via a network 726 (e.g., an Ethernet connection, a digital subscriber line (DSL), a telephone line, coaxial cable, a cellular telephone system, etc.).
[0064] The processor platform 700 of the illustrated example also includes one or more mass storage devices 728 for storing software and/or data. Examples of such mass storage devices 728 include floppy disk drives, hard drive disks, compact disk drives, Blu-ray disk drives, RAID systems, and digital versatile disk (DVD) drives.
[0065] The coded instructions 732 of FIGS. 4, 5 , and/or 6 may be stored in the mass storage device 728 , in the volatile memory 714 , in the non-volatile memory 716 , and/or on a removable tangible computer readable storage medium such as a CD or DVD.
[0066] From the foregoing, it will be appreciate that examples disclosed herein dynamically (e.g., without intervention from a user) scale monitoring of services executing on virtual machines implementing multi-tiered applications. In such examples, user error and oversight are minimized by detecting installation of important services so that, for example, the important services are monitored in the dynamic environment.
[0067] Although examples herein disclose managing monitoring agents without user intervention, alternatively, some limited user intervention (e.g., entering credentials, starting and/or stopping the automated installation of monitoring agents, starting and/or stopping automation software, starting and/or stopping automated services, starting and/or stopping computing devices, etc.) may be used without departing from the scope of the disclosure. For example, a user may intervene to start the VIN 112 of FIG. 1 which may then monitor the computing unit(s) 104 ( FIG. 1 ) in the deployment environment 108 ( FIG. 1 ) and install and/or remove the monitoring agent 102 ( FIG. 1 and/or 2 ) without user intervention.
[0068] Although certain example methods, apparatus and articles of manufacture have been disclosed herein, the scope of coverage of this patent is not limited thereto. On the contrary, this patent covers all methods, apparatus and articles of manufacture fairly falling within the scope of the claims of this patent.
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Methods and apparatus to manage a dynamic deployment environment including one or more virtual machines. A disclosed example involves: (a) automatically scanning the virtual machines in the deployment environment to identify a service installed on any of the virtual machines; (b) automatically determining whether the identified service corresponds to a service monitoring rule; (c) when the service corresponds to the service monitoring rule, automatically determining whether a monitoring agent identified by the service monitoring rule is installed on the virtual machines on which the service is installed; (d) when the monitoring agent identified by the service monitoring rule is not installed on the virtual machines on which the service is installed, automatically installing the monitoring agent on the virtual machines on which the service is installed; and (e) when the monitoring agent identified by the service monitoring rule is installed on the virtual machines on which the service is installed, automatically configuring the monitoring agent to monitor the service in accordance with the service monitoring rule on the virtual machines on which the service is installed, wherein (a), (b), (c), (d) and (e) are repeatedly performed without human intervention.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This patent application claims the benefit of U.S. provisional patent application No. 61/008,283 filed 18 Dec. 2007 which application is included herein in its entirety by reference.
BACKGROUND OF THE INVENTION
[0002] Methods and apparatus for cooling vehicle motors are disclosed in the art.
[0003] WO 2007107489 to Moreau et. al. discloses a fan propeller for cooling a vehicle engine or motor, placed in front of or behind the engine cooling radiator. The invention is concerned with reducing weight and improving performance by having specific thickness profile. To this end the fan propeller comprises a hub and blades extending radially outwards from the hub, the blades having a flattened cross-section with an aircraft wing profile including a leading edge and a trailing edge between which is defined a chord. The blade has a relative thickness up to a maximum value (Emax) in the first quarter of the chord length starting from the leading edge, the relative thickness being defined by the ratio between the thickness of the blade and the length of the chord.
[0004] DE 102005003853 to Geiger discloses a gas turbine comprising a compressor, a combustion chamber, and a turbine having at least one generator for generating electrical energy. After switching off the gas turbine for a period of time, each generator is used as an engine to drive the rotor of respective turbine, causing uniform cooling to the rotor.
[0005] DE 4235815 to Mader et. al. discloses a control system in which each wheel on the undercarriage has an air turbine and a brake unit. The output of a compressor can be connected to the turbines via a compressed air line. The air line is in connection, on the wheel side, with the input of a control valve. This has a first output connected to the turbine and a second output connected to the brake. It also has an actuator connected to a control unit. An air powered turbo unit provides the compressed air. The control unit is connected to pressure sensors on the wheel side and the turbo side and is connected to temperature sensors on the wheel side. The invention increases servicing intervals of brake system and increases life and reliability, relieves pilot during landing, and is a light, simple, low power system.
[0006] Electrically-powered motors for rendering an aircraft self-propelled on the ground without the need for turbine thrust have become very desirable as they offer the possibility of lower carbon dioxide emissions, more efficient fuel usage, and reduced noise levels. However, a problem with large aircraft is how to dissipate heat generated by braking, and having additional hardware in the main gear may adversely impact the cooling of the wheels, brakes and motors after a landing event.
[0007] Motors providing high torque at low speeds are known in the art. Specifically, such motors are known that are designed for the purpose of propelling aircraft on the ground.
[0008] WO05112584 to Edelson discloses a motor-generator machine comprising a slotless AC induction motor. The motor disclosed therein is an AC induction machine comprising an external electrical member attached to a supporting frame and an internal electrical member attached to a supporting core; one or both supports are slotless, and the electrical member attached thereto comprises a number of surface mounted conductor bars separated from one another by suitable insulation. An airgap features between the magnetic portions of core and frame. Electrical members perform the usual functions of rotor and stator but are not limited in position by the present invention to either role. The stator comprises at least three different electrical phases supplied with electrical power by an inverter. The rotor has a standard winding configuration, and the rotor support permits axial rotation.
[0009] WO2006002207 to Edelson discloses a motor-generator machine comprising a high phase order AC machine with short pitch winding. Disclosed therein is a high phase order alternating current rotating machine having an inverter drive that provides more than three phases of drive waveform of harmonic order H, and characterized in that the windings of the machine have a pitch of less than 180 rotational degrees. Preferably the windings are connected together in a mesh, star or delta connection. The disclosure is further directed to selection of a winding pitch that yields a different chording factor for different harmonics. The aim is to select a chording factor that is optimal for the desired harmonics.
[0010] Disclosed in WO2006/065988 to Edelson is a motor-generator machine comprising stator coils wound around the inside and outside of a stator, i.e. toroidally wound. The machine may be used with a dual rotor combination, so that both the inside and outside of the stator may be active. Even order drive harmonics may be used, if the pitch factor for the windings permits them. In a preferred embodiment, each of the coils is driven by a unique, dedicated drive phase. However, if a number of coils have the same phase angle as one another, and are positioned on the stator in different poles, these may alternatively be connected together to be driven by the same drive phase. In a preferred embodiment, the coils are connected to be able to operate with 2 poles, or four poles, under H=1 where H is the harmonic order of the drive waveform. The coils may be connected together in series, parallel, or anti-parallel.
[0011] In U.S. patent application Ser. No. 11/403,402, filed Apr. 12, 2006, a motor-generator machine is disclosed comprising a polyphase electric motor which is preferably connected to drive systems via mesh connections to provide variable V/Hz ratios. The motor-generator machine disclosed therein comprises an axle; a hub rotatably mounted on said axle; an electrical induction motor comprising a rotor and a stator; and an inverter electrically connected to said stator; wherein one of said rotor or stator is attached to said hub and the other of said rotor or stator is attached to said axle. Such a machine may be located inside a vehicle drive wheel, and allows a drive motor to provide the necessary torque with reasonable system mass.
[0012] International Appl. No. PCT/US2006/12483, filed Apr. 5, 2006, discloses a motor-generator machine comprising an induction and switched reluctance motor designed to operate as a reluctance machine at low speeds and an inductance machine at high speeds. The motor drive provides more than three different phases and is capable of synthesizing different harmonics. As an example, the motor may be wound with seven different phases, and the drive may be capable of supplying fundamental, third and fifth harmonic. The stator windings are preferably connected with a mesh connection. The system is particularly suitable for a high phase order induction machine drive systems of the type disclosed in U.S. Pat. Nos. 6,657,334 and 6,831,430. The rotor, in combination with the stator, is designed with a particular structure that reacts to a magnetic field configuration generated by one drive waveform harmonic. The reaction to this harmonic by the rotor structure produces a reluctance torque that rotates the rotor. For a different harmonic drive waveform, a different magnetic field configuration is produced, for which the rotor structure defines that substantially negligible reluctance torque is produced. However, this magnetic field configuration induces substantial rotor currents in the rotor windings, and the currents produce induction based torque to rotate the rotor.
[0013] PCT application no. WO 2007/103266-A2 to Edelson, filed 2 Mar. 2007, discloses a motor comprising: a fixed member comprising a magnetic core and magnetic windings, having an internal cavity; a driven member inside said fixed member, comprising magnetically conductive materials; said driven member being situated inside, and able to move within, said fixed member, wherein magnetic normal force is induced in said fixed member periodically, whereby said driven member is periodically moved by magnetic force with respect to said fixed member, whereby periodic motion is produced.
BRIEF SUMMARY OF THE INVENTION
[0014] An apparatus for cooling undercarriage components of a self-propelled aircraft undercarriage wheel comprising: at least one self-propelled aircraft undercarriage wheel; at least one drive means for propelling said undercarriage wheel; and preferably at least one wheel brake; whereby said drive means acts as a fan to cool said undercarriage components, which may be brakes, wheels, tire beads, drive means or any other undercarriage components. Said undercarriage wheel may be a nosewheel, main gear or any or several or all wheels in an aircraft.
[0015] A technical advantage of this approach is that any reduced heat flow that comes about as a result of a motor being located adjacent to the wheel is overcome by running the disengaged motor as a fan cooler. This is achieved without additional added weight or an increased space requirement in the under-carriage bay.
[0016] A further technical advantage of this approach is that with the cooling means in operation, the brake-cooling rate will be considerably increased and the turn-round time will be reduced.
[0017] A further technical advantage is that the peak temperatures of the tire beads and hydraulic fluid will be reduced below critical values.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0018] The present invention and its technical advantages can be better understood with reference to the following drawings in which:
[0019] FIG. 1 shows the first embodiment of the invention with fan blades.
[0020] FIG. 2 shows the first embodiment of the invention with air tunnels.
DETAILED DESCRIPTION OF THE INVENTION
[0021] An apparatus for cooling undercarriage components of a self-propelled aircraft undercarriage wheel comprising: at least one self-propelled aircraft undercarriage wheel; at least one drive means for propelling said undercarriage wheel; and preferably at least one wheel brake; whereby said drive means acts as a fan to cool said undercarriage components, which may be brakes, wheels, tire beads, drive means or any other undercarriage components.
[0022] Said undercarriage wheel may be a nosewheel, main gear, or any or several or all wheels in any aircraft. Said drive means is preferably one of the motors disclosed in the background section of this patent, since these are designed to have properties suitable for driving an aircraft. Said drive means may also be any high phase order, mesh connected electric induction motor. An advantage of this is that such motors are lightweight, and provide high torque at low speed, as is needed to pull an aircraft. Alternatively, said drive means may be an induction motor, switched reluctance motor, permanent magnet motor or other drive means.
[0023] Said wheel brake may be a disc brake, drum brake, hydraulically activated brake, electrically activated brake, or any brake known in the art.
[0024] In a first embodiment of the present invention, shown in FIG. 1 , said drive means comprises a rotor 102 and a stator 100 , mounted on undercarriage wheel 108 and rotationally mounted on axle 106 . When said rotor is spun, cooling automatically occurs. Said rotor may be shaped like a fan with fan blades 104 (thus having an integral fan), such that air is circulated near said brakes. Alternatively a fan may be mounted on said rotor. Alternatively or additionally, said rotor may comprise holes or tunnels 210 as shown in FIG. 2 , such that air from a cooler location, such as the atmosphere adjacent any outer face of the undercarriage assembly, is brought close to said brakes and circulated around said brakes when said rotor spins. FIG. 2 also shows stator 200 and rotor 202 mounted on undercarriage wheel 208 and axle 206 . Furthermore, air pipes or heat pipes may carry air from a cooler location such as an air conditioning unit or other cool location, and bring said air close to said brakes in order that more cooling occurs when the air is circulated.
[0025] Said holes or tunnels may be provided specifically for cooling or may be provided to perform other functions such as providing a space for a valve stem of a tire or in other ways enabling access to the undercarriage equipment for maintenance. It should be noted that the motor components themselves preferably remain sealed from air, water, dust or other atmospheric conditions while the external shape of the rotor performs cooling. Since even a sealed motor radiates heat in operation, cooling is still necessary.
[0026] Said rotor may be disengaged from said wheel for spinning and the apparatus may further comprise engagement/disengagement means for this purpose, as well as sensing means and control means for spinning the rotor as described in the second embodiment below.
[0027] The figures are given as examples only and are not intended to be limiting. It will be readily understood that many other arrangements and configurations will be possible that will be covered by the scope of this patent, for example, a rotor inside a stator, multiple stators or rotors, eccentric rotors, etc.
[0028] The apparatus may further comprise gears or gear trains as known in the art, or other means for modifying or adapting the speed and/or torque of the drive means with respect to the wheel or cooling means. This includes the use of gears or gear trains, torque converters, planetary gear transmissions, cycloidal reducers, clutches and other known speed and torque transmission means. Said gear, gear train or other transmission means may be separate from or integral to the motor.
[0029] In a second embodiment, said rotor can be engaged and disengaged from cooling apparatus. Said cooling apparatus is preferably a fan with fan blades directing air towards the brakes. Holes, tunnels or pipes may direct cooler air to the brakes as described in the previous embodiment. When said rotor is engaged with the fan, it spins the fan and cools the brakes. Said cooling means may be any other means for cooling an undercarriage component.
[0030] The apparatus preferably comprises fan engagement/disengagement means for engaging and disengaging the cooling means (from/with the wheel and/or the drive means), and drive means controls for turning on the drive means and thus spinning the rotor. Thus, during descent, said rotor might be disengaged from said cooling means, and upon landing, the rotor would be engaged with the cooling means ancomponents have cooled, the rotor may be stopped and disengaged. The rotor can then be engaged with the undercarriage drive means and used to drive the aircraft on the ground. Alternatively, said rotor may be engaged with said cooling means during landing but not spun. These sequences of events are given as examples and any other sequence of events in the spirit of the invention may also be used. For example, said cooling means may operate at the same time as the drive means.
[0031] Said engagement/disengagement means may comprise a clutch system or any other means for engaging or disengaging known in the art.
[0032] The rotor and cooling means may be engaged and disengaged manually by use of an engagement control which may be a push button, switch or the like, in the cockpit, at the gate, or at another useful location. Alternatively or additionally, sensing means may be disposed on the aircraft for sensing when the aircraft is descending, grounded, braking after landing, stopped after landing, the brakes or other components are sufficiently cooled, or any combination of the above. These sensing means may include altitude sensors, temperature sensors, or speed sensors as known in the art or any sensors known in the art that will work for this purpose. The sensing means may be used to sense when the rotor should be engaged with the cooling means and spun, and to automatically do so. For example and without limitation, an altitude sensor may sense that the aircraft is grounded, a speed sensor may sense that the aircraft is stopped, and after this combination of events, a signal may be sent using a logic control to the engagement/disengagement means to engage the rotor automatically, and a signal to the drive means controls to turn on the drive means and spin the rotor. Later a temperature sensor may detect that the brakes have cooled sufficiently, and send a signal via a logic control to the engagement/disengagement means to disengage the rotor automatically, and a signal to the drive means controls to turn off the drive means.
[0033] Alternatively, the sensing means may display a light, symbol or other status display to the pilot, ground staff or other aircraft controller to inform them of the status of the aircraft in order that they can manually engage/disengage the rotor and the cooling means and spin or stop them as required.
[0034] All other features are as in the first embodiment.
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The present invention provides a means for cooling the brakes of under-carriage wheels by disengaging and spinning the motor used to provide traction on landing, thereby providing fan cooling of the brakes.
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CROSS-REFERENCE OF RELATED APPLICATION
The present invention claims the priority under 35 U.S.C. §119 of German Patent Application No. 196 16 275.0 filed on Apr. 24, 1996, the disclosure of which is expressly incorporated by reference herein in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an adjustable deflection roll having a roll sleeve supported on a support beam by a plurality of support devices or units. The support devices may include pressure chambers, positioned between a respective support device and the support beam, and each pressure chamber may be coupled to a supply line.
2. Discussion of Background Information
Adjustable deflection rolls similar, in general, to the roll discussed above may also be referred to as bending-adjusting rolls and may be used in roll machines, e.g., calenders or glazing rolls, to exert pressure on a continuous sheet of material, e.g., paper. In use, the adjustable deflection roll and a paper cylinder form a roll gap or nip through which the material sheet is guided. To maintain an application of pressure in as even a manner as possible across a width of the roll gap, i.e., transverse to a feed direction of the material sheet, the support units are designed to adjust pressure conditions along the extent of the roll gap. The support units, which are pressurized by a hydraulic fluid, e.g., hydraulic oil, may be of conventional design in the art.
To distribute the pressure as precisely, and evenly, as possible, it is desirable to control the support devices individually or at least in small groups. For this purpose, a large number of supply lines is required. Of course, as the number of supply lines increases, the width of the rolls correspondingly increases. Further, the supply lines have to be routed through the support beam. However, because there is only limited space available, cross sections of individual supply device should not exceed a certain predetermined value. For example, larger cross sections would adversely effect the support device, e.g., weaken the support device, such that it would be unable to perform its requisite support functio.
While the above-noted drawbacks do not generally lead to problems in control of pressure distribution, problems do arise in the so-called quick release processes of the roll machines. That is, the hydraulic fluid in rolls exhibiting sleeve lift, i.e., the support devices exert an upward pressure on the inside of the roll sleeve or jacket, has to be removed from the pressure chambers as quickly as possible, e.g., to relieve the support units or to quickly lower the roll sleeve. However, quick release processes cannot be satifactorily achieved due to small diameters of the supply lines.
SUMMARY OF THE INVENTION
An object of the present invention may be to facilitate rapid discharge of the pressure chambers while ensuring a precise distribution of pressure.
This object may be achieved with an adjustable deflection roll of the type discussed above, in which each pressure chamber may be coupled to a supply line and to a drain channel. The drain channel may be closable with a drain valve.
Thus, in accordance with the present invention, pressure release is no longer dependent upon the supply line. Instead, a hydraulic fluid may be removed from the pressure chamber through the drain channel. To ensure that fluid removal occurs only desired, i.e., not during normal roll operation, a drain valve may be utilized to precisely control discharging pressure from the pressure chambers.
The drain channel may preferably lead into a reservoir formed between the roll sleeve and the support beam. Oil that reaches the reservoir, e.g., via hydrostatic support devices, may be continuously drained from the pressure chamber so that the reservoir between the roll sleeve and the support beam may not be filled with oil, and thus, may remain, for the most part, depressurized. Therefore, when the drain valve is opened, the pressurized oil may be pushed out of the pressure chamber and into the reservoir between the roll sleeve and support beam. A preceding pressure reduction, as would otherwise be necessary in the supply lines, is not required by the present invention.
It may be preferred that provide the drain channel with a lower flow resistance than the supply line. This may generally be accomplished by designing the drain channel to have a shorter length than the supply line. In addition, the drain channels may be designed to have a larger cross sectional flow area than the supply line.
Each pressure chamber may preferably have its own supply line and its own drain channel. Alternatively, it may be sufficient to combine individual support devices and, thus, to group individual pressure chambers and to control the support devices in groups. However, it is easier to control the pressure distribution along the width of the deflection roll if each support device is equipped with its own supply line. Further, the pressure release may occur at a higher speed in individually supplied support devices because the hydraulic fluid may be directly drain from each pressure chamber.
The drain channel may preferably branch out from an intermediate channel formed between the pressure chamber and the supply line. Thus, design modifications in an area of the pressure chamber may not be required. In particular, flow conditions that have proven effective may be left unchanged. Further, it may only be necessary to route an additional channel into the support beam.
It may be advantageous to configure the drain valves such that at least a portion of their bodies lie on an exterior of the support beam. This configuration may simplify the manufacturing process. In particular, movable parts may be placed in one housing that is mounted on an outside of the support beam, thus, avoiding extensive modifications to the support beam.
It may be especially advantageous to offset the drain valves by approximately 90° relative to a position of the support devices. In this position, the drain valves may cause the least possible hindrance to a lifting motion of the roll sleeve because there is practically no restriction on the motion of the roll sleeve.
Each drain valve may be actuated at the same time. Thus, when a quick release procedure is required, one command may be sufficient to induce or actuate the pressure release from each of the pressure chambers.
It may be particularly advantageous if each drain valve has a common actuating device. This actuating device may then ensure that actuation of the drain valves by, e.g., by a mechanical actuation, may be synchronized.
The actuating device may be designed as a slider. A slider of the sort contemplated by the present invention may be easily mounted on the support beam and may be actuated from one end. This arrangement may particularly hold true when the slider is arranged to move substantially parallel to an axis the support beam. Such axial motion may be easily controllable from one of the axial ends of the support beam.
The slider may be preferably driven by a piston-cylinder device. A piston-cylinder device of this type may also be operated with the hydraulic fluid that utilized in the adjustable deflection roll. Accordingly, no additional pressure generating mechanisms may be needed.
An alternative slider, which may be designed as a piston located at least on one end of the roll, may be arranged to slide inside a cylinder, is particularly advantageous. This particular alternative may facilitate the manufacturing process. That is, no connection may be required between the slider and the piston of the piston-cylinder unit because it is already provided by the slider itself. Further, the piston may be designed as a plunger piston.
The drain valves may be preferably designed as sliding valves with valve sliders. A flow path may be opened by pushing a through-hole in the valve slider over a corresponding opening of the drain channel. When these two openings do not align, the drain valve is closed. Such a valve design is easily constructed and it also relatively easy to actuate.
In another alternative, the valve sliders of the drain valves may be preferably attached to each other in the axial direction. This renders unnecessary a separate slider and the valve slider becomes the actuating device.
In a different embodiment, each drain valve may exhibit a stopper that may be moved into an opening of the drain channel. There the stopper either may come to rest on a front surface to create a seal, or may be guided into the opening to act as a plug and provides an adequate seal. An absolute seal may not be required in most instances because the support devices themselves exhibit a certain leakage.
It may be preferred that the sliders act on the stoppers through an inclined plane. The axial movement may then be easily converted into a radial movement of the stoppers.
The drain valves may be preferably designed as self-opening valves. This may provide an additional safety feature. For example, if an outage in the supply unit occurs, and no pressure is available in the piston-cylinder unit, the valves open, causing a quick release of the calender roll. If the valves were controlled in an opposite manner, such a quick release could not be guaranteed after an outage of the supply system.
Accordingly, the present invention may be directed to an adjustable deflection roll that may include a roller sleeve; a support beam including a plurality of support devices; the plurality of support devices supporting the roller sleeve; an pressure chamber positioned between the support devices and the support beam; a supply line coupled to each pressure chamber; a drain channel coupled to each pressure chamber; and a drain valve for closing each of the drain channels.
According to a further feature of the present invention, a reservoir may be formed between the roll sleeve and the support beam and the drain channel may lead into the reservoir
According to a further feature of the present invention, the drain channel may exhibit a lower flow resistance than the supply line.
According to another feature of the present invention, each pressure chamber may include a respective supply line and a respective drain channel.
According to still another feature of the present invention, an intermediate channel may be formed between the pressure chamber and the supply line and the drain channel may branch from the intermediate channel.
According to a further feature of the present invention, the drain valves, which may include drain valve bodies, may be mounted with at least a portion of the drain valve bodies on an exterior of the support beam.
According to a still feature of the present invention, the drain valve may be offset approximately 90° from a position of the support unit.
According to a another feature of the present invention, each of the drain valves may be actuated at a same time. Further, a common actuating device may be utilized for actuating each of the drain valves.
According to a further feature of the present invention, the common actuating device may include a slider. Further, the slider may be movable substantially parallel to an axial direction of the support beam.
According to a another feature of the present invention, the slider may include a piston-cylinder unit for driving the common actuating device. Further, at least one end of the slider may include a piston arranged for sliding within a cylinder.
According to a still further feature of the present invention, the drain valves may include slide valves having valve sliders. Further, the valve sliders may be coupled to each other in an axial direction.
According to still another feature of the present invention, each drain valve may include a movable stopper movable into an opening of the drain channel. Further, the slider may act on the stoppers through an inclined plane.
According to yet another feature of the present invention, the drain valves may include self-opening valves.
The present invention may be directed to an adjustable deflection roll that may include a support beam; at least one fluid supply line for supplying a fluid; at least one pressure chamber formed in the support beam coupled to the at least one fluid supply line; and a drain valve coupled to the support beam for draining fluid from the at least one pressure chamber.
According to another feature of the present invention, at least one intermediate channel may couple the at least one fluid supply line to the at least one pressure chamber and at least one drain channel may couple the at least one intermediate channel to the drain valve.
According to another feature of the present invention, the drain valve may be coupled to a plurality of drain channels and the drain valve may selectably closing each drain channel at a same time.
According to another feature of the present invention, the drain valve may include a common valve slider that is slidable within a plurality of spaced valve bodies and each of the spaced valve bodies may be coupled to an exterior portion of the support beam.
According to still another feature of the present invention, a cylinder may be coupled to the exterior portion of the support beam, the common valve slider may include a plurality of notched sections spaced to correspond with each of the drains channels, and the common valve slider may be actuatable by a piston/cylinder arrangement. An end of the common valve slider may include a piston engagable with the cylinder.
According to a further feature of the present invention, a radially actuatable stopper may be associated with each drain channel, the drain valve may include a slider, and each stopper may be actuated at a same time by the slider.
According to a still further feature of the present invention, each stopper may include an angled portion for contacting the slider and the slider may include a complementary angled portion corresponding to each angled portion of the stoppers.
Other exemplary embodiments and advantages of the present invention may be ascertained by reviewing the present disclosure and the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention may be further described in the detailed description with follows, in reference to the noted plurality of drawings by way of non-limiting examples of preferred embodiments of the present invention, in which like reference numerals represent similar parts throughout the several views of the drawings, and wherein:
FIG. 1 illustrates a schematic axial portion of an adjustable deflection roll;
FIG. 2 illustrates a schematic cross section of the adjustable deflection roll;
FIG. 3 illustrates a first embodiment of the drain valves according to the present invention; and
FIG. 4 illustrates a second embodiment for the drain valves according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The particulars shown herein are by way of example and for purposes of illustrative discussion of the preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for the fundamental understanding of the invention, the description taken with the drawings making apparent to those skilled in the art how the invention may be embodied in practice.
FIG. 1 illustrates an end portion of an adjustable deflection roll 1. Adjustable deflection roll 1 may include a roll sleeve or jacket 2 supported by a plurality of support devices 3 on a support beam 4. Support beam 4 may also be referred to as an axle of adjustable deflection roll 1. In this particular case, adjustable deflection roll 1 may be designed as a sleeve lift roll, i.e., support devices lift or raise roll sleeve 2 by exerting a pressure on an inside surface of roll sleeve 2.
Each support device 3 may include a pressure chamber 5 that may be individually pressurized with pressure fluid, e.g., hydraulic oil. Pressure chamber 5 may be positioned between support device 3 and support beam 4. For this purpose, a supply line 6 may be provided for each pressure chamber 5. The pressure in the pressure chambers 5 may be regulated by supply lines 6, which may be formed into a bundle of conduits 7 that may be housed in a main boring 8 of support beam 4.
Main boring 8 may be coupled to pressure chambers 5 via intermediate channels 9. To enable individual control of each pressure chamber 5, partitioning walls 10 having seals 11 may be respectively arranged in main boring 8 between openings of intermediate channels 9. A respective supply line 6, i.e., associated with intermediate channel 9, may end at each partitioning wall 10. FIG. 2 illustrates a cross-section of the adjustable deflection roll through one of the intermediate channels, and, thus, does not show an end of a supply line.
Counter units 12 may be located on a side of the adjustable deflection roll opposite support units 3. Counter units 12 may be pressurized, e.g., with hydraulic fluid, to enable a faster lowering of roll sleeve 2 and to relieve stresses on the roll ends.
Movable arrays of seals and bearings, as are generally known from adjustable rolls utilizing sleeve lift, may be fitted onto the end of the rolls.
As depicted in FIG. 2, a drain channel 14, which may be closed via a drain valve 15, may branch off of intermediate channel 9. Drain valve 15 may be, e.g., as shown in the figure, depicted in the open position.
Drain valve 15 may include a valve housing 16 mountable on an outside of support beam 4. Drain valve 15 may be offset, e.g., approximately 90° relative to support unit 3. Thus, when roll sleeve 2 is lowered, drain valve 15 does not interfere with the lowering, even if it is mounted on the exterior of support beam 4, as shown.
When drain valve 15 is opened, drain channel 14 leads or empties into a reservoir or annulus 17 between roll sleeve 2 and support beam 4. Oil and other hydraulic fluid may flows continuously into reservoir 17, particularly when the adjustable deflection roll utilizes hydrostatic support units 3, and the fluid must be removed to lower roll sleeve 2. Since oil may be continuously drained from, or pumped out of, reservoir 17, the pressure prevailing within reservoir 17 may be practically tank pressure. Therefore, hydraulic fluid that may be pushed out of pressure chamber 5 through drain channel 14 may drain, i.e., substantially without back pressure, into reservoir 17.
Drain channel 14 may be relatively short because it is only necessary that it extend from intermediate channel 9 to reservoir 17, i.e., to the circumferential outer wall of support beam 4. Accordingly, even if a cross section of drain channel 14 is as big as a cross section of a supply line 6, the flow resistance through drain channel 14 is substantially lower due to the shorter length of travel. Thus, as soon as drain valve 15 is opened, the hydraulic fluid may escape quickly from the pressure chambers 5.
Support units 3 may be generally known to those ordinarily skilled in the art. Thus, for the sake of clarity, supply lines and throttles generally associated support unit such as support unit 3 have not been depicted in the drawings. Thus, support unit 3 may e.g., include an annular piston so that pressure chamber 5 may also include an annular shape. Alternatively, support unit 3 may also include two pistons, as shown in FIG. 2, or may utilize a design such as depicted in FIG. 1. However, the precise design of individual support units 3 is up to the system designer or engineer. However, in accordance with the present invention, it is necessary that the hydraulic fluid, utilized to pressurize support unit 3 during normal operation, may quickly escape through drain channel 14 and drain valve 15 upon quick release of the adjustable deflection rolls.
FIGS. 3 and 4 illustrate exemplary designs for drain valve 15. A first embodiment of a drain valve, shown in FIG. 3, may be designed as a sliding valve 18. In FIG. 3, the position of sliding valve 18 is illustrated as closed.
Each sliding valve 18 may include a common valve slider 19 having a through-hole 20 for each drain valve. With valve slider 19 in the position shown in FIG. 3, through-holes 20 are not aligned with drain channel 14, thus closing and sealing the end of drain channel 14, i.e., the hydraulic fluid cannot drain through or around common valve slider 19. Acting together with common valve slider 19, a valve housing 16 may seal or close the opening of drain channel 14. However, by sliding common valve slider 19 in a direction 33, through-hole 20 may be moved to align with drain channel 14 and enable the free flow of hydraulic fluid pressure chamber 5.
Valve sliders 19 may be driven by two piston-cylinder units 21, 22 located at each axial end of the common valve slider 19. The common valve slider 19 may be modified on both ends so that common valve slider 19 itself may act as piston 23, 24, which is positioned within a cylinder 25, 26, respectively. When cylinder 25, i.e., piston-cylinder unit 21, is pressurized, common valve slider 19 may be shifted toward the right, i.e., in direction 32, to close slider valves 18. When cylinder 26, i.e., piston-cylinder unit 22, is pressurized, common valve slider 19 may be shifted to the left, in direction 33, to opens drain valves 15 (slider valves 18). The same hydraulic fluid used to raise or adjust the pressure of support units 3 may be utilized to actuate piston-cylinder units 21, 22.
Instead of piston-cylinder unit 22, which may be used to open sliding valves 18, a spring may be utilized that opens sliding valves 18 when a pressure in piston-cylinder unit 21 is lowered. Thus, sliding valves 18 may be automatically opened in the absence of this hydraulic pressure.
FIG. 4 illustrates an alternative design for drain valves 15 which may include a stopper 27 that may be guided into opening of drain channel 14 in the manner of a reciprocating plug. FIG. 4 illustrates drain valves 15 in an open position. Stopper 27 may be pushed into its open position by a pressure spring 28 and hydraulic fluid may be drained from drain channel 14, i.e., around stopper 27 into a chamber 29, from which it reaches the reservoir 17 between roll sleeve 2 and support beam 4 in a manner that is not illustrated here.
Stopper 27 may be actuated by an inclined plane 30 formed within slider 31 that may slide substantially parallel to support beam 4 in an axial direction, e.g., as shown by arrows 32, 33. When slider 31 is moved in a direction of arrow 32, drain valves 15 are closed. Conversely, when slider 31 is moved in a direction of arrow 33, drain valves 15 are opened.
To close the drain valves 15, a left end of slider 31 may be equipped with a piston-cylinder unit 21 which may be pressurized with hydraulic fluid, i.e., in a manner similar to that discussed with regard to FIG. 3. When slider 31 is then moved to the right, the inclined surfaces 30 of slider 31 and stopper 27 move stopper 27 radially inward, thus, closing the opening of drain channel 14.
In an alternative embodiment, stopper 27 may also act on a front surface that surrounds the opening of drain channel 14. However, the valve arrangement illustrated in FIG. 4 may also guarantees a good seal of drain valve 15.
Common valve stopper 13 is depicted in FIG. 3, as well as the slider 31 in FIG. 4 may include several, similarly designed parts. In particular, the parts may be screwed together. If necessary, spacing pieces could be positioned between individual slider parts. With this configuration, the mechanical connection of the individual parts ensures that all valves 15, 18 may be opened and closed at a same time.
It is noted that the foregoing examples have been provided merely for the purpose of explanation and are in no way to be construed as limiting of the present invention. While the invention has been described with reference to a preferred embodiment, it is understood that the words which have been used herein are words of description and illustration, rather than words of limitation. Changes may be made, within the purview of the appended claims, as presently stated and as amended, without departing from the scope and spirit of the invention in its aspects. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein; rather, the invention extends to all functionally equivalent structures, methods and uses, such as are within the scope of the appended claims.
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An adjustable deflection roll including a roll sleeve or jacket supported by a plurality of support devices positioned partially within a support beam. Pressure chambers may be located between the support devices and the support beam and each pressure chamber may be coupled to a supply line. As the length of the roll increases, and as the need for increasingly more precise pressure distributions also increases, more support devices may be utilized. The adjustable deflection roll may also include a drain channel to facilitate quick relief of the pressure chambers when necessary. To accomplish this, each pressure chamber may be coupled to the drain channel furnished with the supply line such that the drain channel may be closed with a drain valve.
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TECHNICAL FIELD
[0001] The present invention relates to the field of power supply for radar systems.
BACKGROUND ART
[0002] Switched power conversion results in electromagnetic interferences (EMI). To prevent the power conversion from disturbing other electronic equipment, certain requirements for maximum allowed interference levels have to be met. These interferences are measured over a frequency interval. One solution to reduce the interferences to allowable levels is to use filters. Another solution is to spread the energy of the interference over a broad frequency interval, through frequency modulation of the switching frequency. Such a solution is known from U.S. Pat. No. 4,190,882.
[0003] The problem with the first solution is that filter components tends to be large and heavy. The problem with the second solution is that, although the amplitude of the spread-out switching frequency band is substantially decreased, the frequency modulated switching still runs the risk of disturbing the function to which the converted power is intended to be used, e.g. a radar function if the modulation frequency is transferred further in the radar system. A radar is intended to discover electromagnetic radiation, and due to the Doppler effect, it is not known which frequency a received signal will have if you have moving objects within the coverage of the radar. The switching frequency or its harmonics or sub harmonics can therefore be mistaken for a moving object.
[0004] There is thus a need to accomplish an improved radar system comprising a switching mode power converter, which is not based on large and heavy filter components, and in which the switching frequency or its harmonics or sub harmonics will not be mistaken for a moving object by the radar unit.
SUMMARY
[0005] The object of the invention is to provide an inventive radar system, and a method of reducing the noise picked-up by a radar unit and generated by a switching mode power converter, where the previously mentioned problems are avoided. The object is achieved by a radar system comprising a switching mode power converter, wherein a pulse radar unit is configured to transmit RF pulses with a pulse repetition frequency. The power converter further comprises a switching controller, which is configured to control at least one switching element. The switching controller is also configured to receive a frequency modulated input signal, wherein the modulation frequency of said input signal is configured to be derived from the pulse repetition frequency of the radar unit.
[0006] The object is further achieved by a method of reducing the noise picked-up by a radar unit and generated by a switching mode power converter, whereby the radar unit transmits RF pulses with a pulse repetition frequency, comprising the steps of:
controlling at least one switching element be means of a switching controller; supplying a frequency modulated input signal to the switching controller;
and wherein the modulation frequency of said input signal is derived from the pulse repetition frequency of the radar unit.
[0009] Further advantageous aspects of the invention are provided by the dependent claims.
[0010] According to an aspect of the invention, a pulse repetition frequency signal carrying the pulse repetition frequency of the radar unit is configured to be supplied from the radar unit to the power converter.
[0011] According to an aspect of the invention, a signal carrying the pulse repetition frequency, or an integer multiple thereof, is supplied to a frequency modulator, which is configured to generate the frequency modulated input signal.
[0012] According to an aspect of the invention, the pulse repetition frequency signal is supplied to a first waveform generator, which is configured to generate a modulating signal having a modulating frequency derived from said pulse repetition frequency, and wherein a second waveform generator is configured to generate a base switching signal having a centre frequency, and wherein the base switching signal and the modulating signal are supplied to a frequency modulator, which is configured to generate a frequency modulated input signal having a centre frequency from the base switching signal and a modulation frequency from the modulating signal.
[0013] According to an aspect of the invention, the frequency of the pulse repetition frequency signal is configured to be multiplied with an integer n in a frequency multiplier before being supplied to a frequency modulator.
[0014] According to an aspect of the invention, the frequency of the pulse repetition frequency signal is configured to be multiplied with an integer n in a frequency multiplier before or after being supplied to a waveform generator, such as to generate a modulating signal having a modulating frequency which is an integer multiple of the pulse repetition frequency.
[0015] According to an aspect of the invention, the switching controller is a pulse width modulator.
[0016] According to an aspect of the invention, the relationship between the modulating frequency and the centre frequency, which determines the spread of the switching frequency bands, is between 3-15%.
[0017] According to an aspect of the invention, the method of reducing the noise picked-up by a radar unit comprises supplying a pulse repetition frequency signal carrying the pulse repetition frequency of the radar unit from the radar unit to the power converter.
[0018] According to an aspect of the invention, the method of reducing the noise picked-up by a radar unit comprises supplying the pulse repetition frequency of the radar unit, or an integer multiple thereof, to a frequency modulator, which generates the frequency modulated input signal.
[0019] According to an aspect of the invention, the method of reducing the noise picked-up by a radar unit comprises supplying the pulse repetition frequency signal to a first waveform generator, which generates a modulating signal having a modulating frequency derived from said pulse repetition frequency; generating a base switching signal having a centre frequency in a second waveform generator; and supplying the base switching signal and the modulating signal to a frequency modulator, which generates a frequency modulated input signal having a centre frequency from the base switching signal and a modulation frequency from the modulating signal.
[0020] According to an aspect of the invention, the method of reducing the noise picked-up by a radar unit comprises multiplying the frequency of the pulse repetition frequency signal with an integer n in a frequency multiplier before supplying said pulse repetition frequency signal to a frequency modulator.
[0021] According to an aspect of the invention, the method of reducing the noise picked-up by a radar unit comprises multiplying the frequency of the pulse repetition frequency signal with an integer n in a frequency multiplier before or after supplying said pulse repetition frequency signal to a waveform generator, such as to generate a modulating signal having a modulating frequency which is an integer multiple of the pulse repetition frequency.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] The present invention will now be described in detail with reference to the figures, wherein:
[0023] FIG. 1 shows a comparison of an unmodulated switching signal as well as a modulated switching signal in the power spectrum as a function of frequency;
[0024] FIG. 2 shows a schematic block diagram of a pulse radar unit according to the invention; and
[0025] FIG. 3 shows a schematic diagram of the switching mode power converter of FIG. 2 according to an example of the present invention.
DETAILED DESCRIPTION
[0026] Switching mode pulse width modulated AC-DC and DC-DC power converters generate considerable amount of conducted and radiated noise and electromagnetic interference (EMI) at the switching frequency and its harmonics and sub harmonics. If a signal is frequency modulated with a constant modulation frequency, the frequency spectra will comprise the modulation frequency as well as sums and differences between this modulation frequency and integer multiples of the modulation frequency.
[0027] Radiated and conducted EMI noise from the power converter will be picked up by and interfere with the operation of adjacent electrical equipment. The method of frequency modulating the switching frequency of the power converter results in the distribution and spreading of the disturbances over a frequency interval. Spread spectrum switching takes the energy concentrated at a small number of frequency points and deliberately spreads it over a wider band of frequencies. This lowers the average value of the peaks of the currents because the total amount of energy in the wave-forms is the same as before. In practice, a narrow band variation in switching frequency of less than 20% is used and is adequate to realise the benefits of spread spectrum switching. Such a limited variation also allows the design and components of the power converter to remain essentially the same. FIG. 1 shows a comparison of the power in dB on y-axis 10 of an unmodulated switching signal as well as a modulated switching signal in the power spectrum as a function of frequency f on the x-axis 11 . Peaks 7 , 8 , 9 indicate the basic switching frequency including two harmonics of the unmodulated switching signal, whereas lower 1 , 3 , 5 and upper 2 , 4 , 6 sidebands centred on said peak switching frequencies f sw , 2 f sw and 3 f sw indicate the frequency modulated switching signal. The actual spectral composition and shape of the sideband depends on the variation of the modulating frequency as well as on the pulse form. Spread spectrum switching thus decreases the need for heavy and large filter components and reduces frequency concentrated EMI.
[0028] Since electromagnetic interference noise will be picked up by and interfere with the operation of adjacent electrical equipment, the switched signal can disturb the function of adjacent electrical equipment to which the converted power is intended to be used.
[0029] The invention is based on the finding that when a frequency modulated switched signal is used to regulate a power converter for a pulse radar unit, the receiver of the radar unit can pick up the electromagnetic interference noise from the power converter, and interpret said interference noise as a signal reflected back from an existing physical object even if said object does not exist in reality.
[0030] There is consequently a need for the radar unit to remove all received signals having the switching frequency of the power converter to omit any non-existing objects. The inventive idea is here to take advantage of the fact that a radar unit due to its inherent design and function already has points of frequencies which it disregards, namely the pulse repetition frequency PRF and its harmonics and sub harmonics. The PRF can be seen as the sampling clock of the system. The harmonics from the power system will be sampled by this clock.
[0031] Any received signal will be folded down to the interval 0 Hz-PRF due to the Nyquist Theorem. If the signal is an integer multiple of the PRF, it will be folded down to 0 Hz. This DC component is filtered and will not be used for target acquisition. Consequently, if the modulation frequency is selected to be identical to the PRF of the radar unit, or an integer multiple thereof, said electromagnetic interference noise from the power converter will be automatically disregarded as well. The switching frequency will therefore neither interfere with the radar unit, nor is there a need for any additional filter components to remove said switching noise.
[0032] FIG. 2 shows an example of a schematic block diagram of a pulse radar unit 20 according to the invention together with a switching mode power converter 21 , which supplies a radar transmitter 22 with power. The power converter can of course supply power to the rest of the radar unit as well. The transmitter 22 generates short duration high-power radio frequency RF pulses of energy that are transmitted via the duplexer 24 to an antenna 23 where they are radiated. The duplexer 24 isolates a receiver 25 from the transmitter 22 while permitting them to share the antenna 23 . Through an amplification process and computer processing, the radar receiver 25 produces information about possible indentified objects. The power converter 21 , transmitter 22 , duplexer 24 and receiver 25 can be controlled by a common control unit 27 .
[0033] An analogue or digital control connection 26 exists between the control unit 27 and the power converter 21 to convey information about the present PRF. Said control connection can of course also be provided between the transmitter 22 and the power converter 21 instead, or any other equipment of the radar unit having information about the PRF. The PRF is a measure of how frequently the RF pulses are transmitted by the radar transmitter 22 .
[0034] This PRF information is the key to the invention since it forms the basis of the modulating signal used to frequency modulate a centre switching frequency in the power converter 21 .
[0035] FIG. 3 shows a schematic diagram of the switching mode power converter 21 of FIG. 2 according to an example of the present invention. ADC input voltage V in is coupled to the source of an n-channel metal-oxide-semiconductor field effect transistor (nMOSFET) 31 , or any other suitable power switching device. This input voltage V in is connected to an output filter, comprising an inductor 32 and a capacitor 33 , by control of a pulse width modulator (PWM) 34 , which thus functions as a switching controller. Switching controller 34 has a first input configured to accept a frequency modulated input signal S in and a first output Q, which provides a preferably square wave signal, having a duty cycle (i.e. ratio of high time to signal period) that determines a DC voltage level at an output V out located at point A. The preferably square wave signal is coupled to the gate of nMOSFET 31 , which is on when the square wave signal is high and off when the square wave signal is low.
[0036] During the time nMOSFET 31 is on, the input voltage V in is coupled to the output filter and a voltage is induced across inductor 32 . When the square wave signal drops from high to low, nMOSFET 31 turns off and a p-channel pMOSFET 35 turns on. When pMOSFET 35 is on, inductor 32 discharges its energy through the radar transmitter (not shown), which is coupled to the output V out . A comparator 36 constantly compares a sample of the voltage at the output V out to a reference voltage 37 and provides a switching controller control signal a second input of the switching controller 34 . Switching controller control signal is used by the switching controller 34 to adjust the duty cycle of the square wave signal at the first output Q and second output Q . Some or all of the above-described components may be integrated in a single integrated circuit.
[0037] According to the present invention, the power converter 21 is configured to receive a PRF signal S PRF from the radar unit 20 with information about the pulse repetition frequency PRF of the radar unit 20 for synchronization purpose. The frequency of the PRF signal S PRF may subsequently be multiplied with an integer n in a frequency multiplier 38 . The frequency multiplied PRF signal is then supplied to a first waveform generator 39 to generate a modulating signal S mod having a modulating frequency, which is an integer multiple of the PRF. The PRF signal S PRF may of course also be supplied to the first waveform generator 39 before being frequency multiplied with an integer n in a frequency multiplier 38 , to generate a modulating signal S mod having a modulating frequency, which is an integer multiple of the PRF. A second waveform generator 41 generates at the same time a base switching signal S bs having a centre frequency.
[0038] The base switching signal S bs is finally supplied to a frequency modulator 40 together with the modulating signal S mod to provide a frequency modulated input signal S in having a centre frequency from the base switching signal S bs and a modulation frequency from the modulating signal S mod . The frequency modulated input signal S in is subsequently supplied to the switching controller 34 to control the switching frequency of the switching transistors 31 , 35 .
[0039] The frequency multiplication factor n is selected to provide a suitable relationship between the modulating frequency and the centre frequency, as this relationship determines the spread of the switching frequency bands. Too high spread has detrimental effect on the controllability of the pulse width modulation, whereas too low spread has little effect on reducing the interference peaks in the power spectrum. As mentioned above, variation in switching frequency of less than 20% is adequate to realise the benefits of spread spectrum switching. Preferably, the variation in switching frequency is between 3-15% to find a balanced solution, where the negative effect of too high and too low variation is minimised. For example, the control signal S PRF to the power converter 21 from the radar unit 20 consists of a 4 kHz signal, which may be frequency multiplied with a factor 3 in the frequency multiplier 38 to become a 12 kHz modulating signal S mod . The base switching signal S bs can have a centre frequency of 150 kHz, which yields a switching frequency spread of 8% of the frequency modulated input signal S in .
[0040] The power converter 21 in FIG. 2 is supplied with DC input voltage V in , but can alternatively be supplied with any type of alternating current AC. If AC is supplied, an input rectifier filter (not shown), possibly represented by a bridge rectifier, can be provided before the nMOSFET 31 , such that the rectified AC is supplied to the nMOSFET. Additionally, the switched power pulses can also be supplied to a step-up high voltage transformer (not shown) so as to attain a higher level of power supply.
[0041] The schematic diagrams depicted in FIGS. 2 and 3 are not restricting the invention to exactly the shown configuration. For example is it not necessary to represent the function or functions of each block present in FIG. 2 by a separate block, but said functions may be included within a more complex block, or divided into a plurality of more simple blocks. Correspondingly, the topology of the power converter shown in FIG. 3 is only for illustrative purposes, and the present invention is equally applicable to any other type of power converter topology, of which numerous types are known from the prior art, for example Buck, Boost, Forward, Full bridge etc. Possible converter configurations are AC-AC, AC-DC, DC-AC and DC-DC. The principles of the invention are equally applicable to both voltage and current regulation. The invention is consequently not limited to the examples described above, but may vary freely within the scope of the amended claims.
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A radar system including a switching mode power converter. A pulse radar unit is configured to transmit RF pulses with a pulse repetition frequency. The power converter includes a switching controller that is configured to control at least one switching element. The switching controller is configured to receive a frequency modulated input signal. The modulation frequency of the input signal is configured to be derived from the pulse repetition frequency of the radar unit.
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FIELD OF THE INVENTION
[0001] The present invention relates to an industrially applicable process for the preparation of methylphenidate hydrochloride of formula I,
[0000]
BACKGROUND OF THE INVENTION
[0002] Methylphenidate (Ritalin) is a psychostimulant drug approved for treatment of ADHD or attention-deficit hyperactivity disorder, postural orthostatic tachycardia syndrome and narcolepsy. It was first licensed by the FDA in 1955 for treating ADHD, prescribed from 1960, and became heavily prescribed in the 1990s, when the diagnosis of ADHD itself became more widely accepted. It is available worldwide with different brand names like Concerta®, Daytrana®, Metadate CD®, Metadate® ER, Methylin®, Quillivant™ XR, Ritalin LA®, Ritalin-SR®, Ritalin®. Here 2-phenyl-2-(piperidin-2-yl) acetamide is key intermediate to prepare methylphenidate or its salts thereof.
[0000]
[0003] Until the introduction of d-threo methylphenidate hydrochloride, dexmethylphenidate hydrochloride, Focalin®) in 2002, all marketed forms of methylphenidate contained a 50:50 racemic mixture of d-threo methylphenidate and 1-threo methylphenidate in the form of the hydrochloride salt. In 2007, a transdermal patch containing racemic dl-threo methylphenidate (Daytrana®) was approved by the FDA.
[0004] U.S. Pat. No. 2,957,880 describes a sequence involving the resolution of the amide derivative of the corresponding erythro isomer, conversion to the threo isomer, followed by the hydrolysis of the amide to the corresponding acid in isolated form, and esterification of the resulting acid with methanol to give methylphenidate.
[0000]
Mixture of threo and erythro isomer of amide
[0005] Patrick, K. S., J. Med. Chem. 24:1237-1240 (1981), discloses the process, according to disclosure, erythro- and threo-dl-2-(4-methoxyphenyl)-2-(2′-pyridyl) acetamide hydrochloride is dissolved in glacial acetic acid and PtO 2 is added into it. Thus, conversion from pyridine to piperidine ring takes place in hydrogen pressure. After evaporation the obtained oil is dissolved in methanol, treated with Norite and filtered and then excess of diethyl ether-HCl is added. The solvent is evaporated to obtain erythro- and threo-dl-2-(4-methoxyphenyl)-2-(2′-piperidyl)acetamide hydrochloride in 72% yield. Further it is treated with hydrochloric acid to obtain erythro- and threo-dl-2-(4-methoxyphenyl)-2-(2′-piperidyl)acetic acid hydrochloride. Alternatively, erythro- and threo-dl-2-(4-methoxyphenyl)-2-(2′-piperidyl)acetamide hydrochloride is treated with 50% potassium hydroxide for 4 days until an aliquot contained no more than 5% erythro isomer. The mixture is cooled and crystallized by ethyl acetate to give 95+% threo isomer and 53% yield. Then it is followed by treatment of 48% hydrobromic acid to obtain hydrobromide salt of corresponding threo-dl-2-(4-hydroxyphenyl)-2-(2′-piperidyl) acetic acid having 95+% threo isomer and 94% yield. The obtained white crystals are treated with methanol-HCl followed by evaporation of solvent and recrystallized with acetone-diethyl ether to get methylphenidate hydrochloride having 73% yield. The overall yield is just around 26% from erythro- and threo-dl-2-(4-methoxyphenyl)-2-(2′-pyridyl) acetamide hydrochloride, which is industrially not advantageous.
[0006] Synthetic methods for preparing racemic mixtures of threo- and erythro-α-phenyl-2-piperidineacetamides as raw materials for the preparation of threo-methylphenidate are described in U.S. Pat. Nos. 2,507,631; 2,838,519; 2,957,880 and 5,936,091; and in J. Med. Chem., 39, 1201-1209 (1996). These methods disclose reduction of the pyridine ring to a piperidine ring by hydrogenation on PtO 2 Pt/C catalyst in glacial acetic acid as a solvent. The reaction takes about 26 hours for the completion.
[0000]
[0007] U.S. Pat. No. 7,459,467 describes the preparation of α-phenyl-α-piperidyl-2-acetamide by treating α-phenyl-α-pyridyl-2-acetamide with 0.1N perchloric acid in acetic acid, Pd/C and alcohol as reaction media under 12-15 Kg/cm 2 hydrogen pressure at 45-50° C. for 15-18 hours. The catalyst is removed by filtration. The filtrate is concentrated under reduced pressure followed by basifying with aqueous sodium hydroxide solution to precipitate α-phenyl-α-piperidyl-2-acetamide. The patent is silent or not disclosing the conversion of α-phenyl-α-piperidyl-2-acetamide to methylphenidate hydrochloride. The patent discloses preparation of methylphenidate free base from α-phenyl-α-pyridyl-2-methyl acetate by using same reaction condition, reagents and solvent for the reduction as mentioned above. The preparation of methylphenidate hydrochloride from methylphenidate obtained in 78%; hence 22% yield loss is uneconomic and isolation of methylphenidate and then converson to corresponding hydrochloride salt adds more unit operations and yield loss as well. The above process for the preparation of α-phenyl-α-piperidyl-2-acetamide is not feasible at large scale because it uses 0.1N perchloric acid which is unsafe, process needs hastelloy autoclave and also has the high pressure 12-15 Kg/cm 2 which is not safe at large volume in autoclave. The process involves tedious and lengthy operation for isolation of α-phenyl-α-piperidyl-2-acetamide. Volumes of solvents are also 11-15 times of input; hence the process is also not environment friendly.
[0008] U.S. Pat. No. 7,229,557 describes the esterification of dl-ritalinic acid in about 20 molar equivalents of methanol saturated with hydrogen chloride gas under reflux. From the reaction, dl-threo methylphenidate hydrochloride was obtained in 37%yield.
[0009] U.S. Patent Application 2010/0179327 describes the preparation of amino acid esters such as methylphenidate. The application describes the reaction of threo-α-phenyl-α-(2-piperidinyl)acetic acid [threo 99.51%: erythro 0.49%], methanolic HCl, and trimethyl orthoacetate with heating at reflux to form methylphenidate in 69.8% yield. As per the disclosure, 69.8% yield of methylphenidate is not viable from the industrial point view, even after taking 99.51% pure threo-α-phenyl-α-(2-piperidinyl)acetic acid.
[0010] PCT application no. 2011/067783 discloses process for the preparation of methylphenidate hydrochloride by reacting α-phenyl-α-piperidyl acetamide with 20% aqueous hydrochloric acid solution and reflux for 2-6 hours. The reaction mixture is cooled and diluted by water to get clear solution followed by extracting with dichloromethane. The layers are separated and pH of aqueous layer is adjusted by adding sodium hydroxide to get threo α-phenyl-α-piperidyl-2-acetic acid in 88.6% yield having isomeric purity [threo 99.9%: erythro 0.1%]. It means the process using very pure α-phenyl-α-piperidyl acetamide to prepare pure threo α-phenyl-α-piperidyl-2-acetic acid. Thus obtained corresponding acid is converted to methylphenidate hydrochloride by treating with thionyl chloride and methanol at temperature below 10° C. The reaction mixture is kept under stirring over night at room temperature followed by distillation of methanol under reduced pressure and then cooled to 10° C. Water and ethyl acetate is added into the residue under constant stirring. The pH is adjusted by using dilute caustic solution and the layers are separated. The solvent is distilled off and treated with IPA-HCl to give methylphenidate hydrochloride.
[0011] PCT application no. 2012/080834 discloses the process for preparing methylphenidate hydrochloride by treating dl-threo ritalinic acid which may be very pure material, with HCl gas in methanol. The reaction mixture is maintained for 20 hours at 41-42° C. Trimethyl orthoformate is added into the reaction mixture in one portion, maintained for 3.5 hours at 41-42° C. and 19 hours at room temperature. The reaction mixture is distilled off and isopropanol is added simultaneously. Subsequently the reaction mixture is cooled to 2° C. for 30 minutes to get methylphenidate hydrochloride. The reagent trimethyl orthophosphate is showing hazards like acute toxicity (oral, dermal, inhalation), skin irritation, eye irritation, skin sensitization and flammable as well. Moreover that use of additional regent like trimethyl orthophosphate in high quantity i.e 2 mole equivalents for the esterification will increase the cost of the product and hazardous for the environment as well as humans. The major negative point of trimethyl orthophosphate is effluent problem; hence it is not preferable for large scale.
[0012] A major drawback of the processes described in above documents is that they all use costly catalyst such as platinum metal adsorbed on carbon or platinum oxide with a very high loading [high loading means higher amounts with respect to the starting compound (II)] for the selective reduction of pyridine ring. Platinum catalysts are known for their high catalytic activity in comparison with milder metal catalyst such as Nickel or Palladium. The order of catalytic activity is Rh>Pt>Pd>Ni. By using Pt or its oxide and Rh catalyst for hydrogenation makes the process uneconomical. Other prior art process involves reduction of pyridine ring by using palladium catalyst with harsh and hazardous reagents, additional solvents, high pressure, lengthy and high cost equipments required, which cumulatively makes the process unattractive for industrial scale.
[0013] A need exists for a more efficient and economical process for the reduction of the pyridine ring and novel approach to prepare methylphenidate hydrochloride in good yield and high purity at industrial scale.
[0014] Thus, present invention fulfills the need of the art and provides an improved and industrially applicable process for reduction of pyridine ring of amide intermediate and/or the preparation of methylphenidate hydrochloride, which provides methylphenidate hydrochloride in high purity, overall good yield and one pot synthesis of methylphenidate hydrochloride from threo-2-phenyl-2-(piperidin-2-yl) acetamide [threo NLT 85%: erythro ˜12%]. The present invention can be described, as shown in scheme 2.
[0000]
OBJECTIVE OF THE INVENTION
[0015] The principal objective of the present invention is to provide an efficient and industrially advantageous process for preparation of methylphenidate hydrochloride.
[0016] Another prime objective of the invention is to provide a process for the preparation of methylphenidate hydrochloride in single step.
[0017] Another leading objective of the invention is to provide an efficient, improved and industrially advantageous process for preparation of methylphenidate hydrochloride which is conveniently applicable to industrial scale and avoiding use of various solvents and operations.
[0018] Further one more objective of the present invention is to provide a novel process for the preparation of mixture of erythro- and threo-2-phenyl-2-(piperidin-2-yl) acetamide.
[0019] Yet additional objective of the present invention is to provide a novel one-pot process for the preparation of methylphenidate hydrochloride from threo-2-phenyl-2-(piperidin-2-yl) acetamide [threo NLT 85%: erythro ˜12%].
[0020] Yet foremost objective of the present invention is to provide a process for the preparation of methylphenidate hydrochloride having high purity and good yield.
SUMMARY OF THE INVENTION
[0021] Accordingly, the present invention provides a novel process for the preparation of mixture of erythro- and threo-2-Phenyl-2-(piperidin-2-yl)acetamide of compound of formula III, process comprises the step of: treating the compound of formula II with reducing agent in acid, except any other solvent to provide a compound of formula III.
[0022] Accordingly, the present invention provides a novel one-pot process for the preparation of methylphenidate hydrochloride of formula I from threo 2-phenyl-2-(piperidin-2-yl)acetamide of formula IV, process comprises the step of: treating compound of formula IV with methanol, in the presence of catalyst and alcoholic hydrochloric acid to form compound of formula I.
[0023] Accordingly, the present invention provides a process for the preparation of methylphenidate hydrochloride of formula I.
[0000]
[0000] which proves to be efficient and industrially viable. The process comprises the steps of:
a). treating the compound of formula II,
[0000]
with reducing agent in acid to provide a compound of formula III;
[0000]
b). treating compound of formula III with an inorganic base to provide compound of formula IV;
[0000]
c). treating compound of formula IV with methanol, in the presence of catalyst and alcoholic hydrochloric acid to provide compound of formula I; and)
d). optionally purifying compound of formula I by treating with suitable solvent.
[0029] Accordingly, the present invention provides a process for the purification of methylphenidate hydrochloride of formula I in alcohol.
[0030] Accordingly, the present invention provides an improved process for the preparation of pharmacopoeial grade methylphenidate hydrochloride.
DETAILED DESCRIPTION OF THE INVENTION
[0031] All ranges recited herein include the endpoints, including those that recite a range “between” two values. Terms such as “about”, “generally” and the like are to be construed as modifying a term or value such that it is not an absolute. Such terms will be defined by the circumstances and the terms that they modify as those terms are understood by those skill in the art. This includes, at very least, the degree of expected experimental error, technique error and instrument error for a given technique used to measure a value.
[0032] The term “NLT” means “not less than” and “NMT” means “not more than” with respect to purity of the compound.
[0033] The present invention provides an improved and efficient process for the preparation of methylphenidate hydrochloride of formula I.
[0034] According to the embodiment of the invention provides an industrially viable process for preparation of methylphenidate hydrochloride starting from compound of formula II.
Stage I:
[0035] The preferred embodiment of the present invention is to provide a process to prepare compound of formula III from compound of formula II. The compound of formula II can be reduced in the presence of reducing agent to form compound of formula III. Generally the reaction involves hydrogenation of compound of formula II in the presence of reducing agent in a solvent at a particular temperature for sufficient time. Reducing agents include palladium on carbon. Solvent includes acid solvent, preferably glacial acetic acid or aqueous acetic acid and the like, except any other solvent. The reaction mixture is heated at 50-70° C. for 1 to 24 hours, preferably at 55-65° C. for about 15 hours under pressure about 4-5 Kg/cm 2 . After completion of the reaction, the mixture is filtered and followed by workup procedure to obtain compound of formula III.
[0036] More precisely, the workup can be done by concentrating the filtrate under vacuum below 80° C. followed by addition of water and treated with activated carbon to decolorize the material. Then after pH can be adjusted using a base. Preferably the pH can be 10-12, more preferably near about 12. The suitable base can be selected from the group comprising of inorganic base. Inorganic base include alkali or alkaline metal hydroxides, carbonates, bicarbonates, alkoxides; wherein inorganic base is preferably sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate; wherein inorganic base is more preferably sodium hydroxide. The base treatment results in precipitation of free base of formula III.
[0037] The principle advantages of this particular stage are the process does not involve costly catalyst like platinum or rhodium catalyst for the reduction. Moreover that the process involves use of acid itself as a solvent and no additional solvents are required; hence the recovery of acid by the distillation and good yield of the product makes the process economical or cost-effective. The recovered acid is achieved in good quality which can be used further without additional purification. In addition, the process become environment friendly because of less effluent and negligible effluent treatment cost. In this way the present invention is ameliorating the major drawbacks of the prior art processes.
Stage 2:
[0038] The compound of formula III can be treated with base to get pure compound of formula IV. The racemic mixture of formula III upon treatment with inorganic base resulted in major threo isomer of formula IV. The inorganic base include alkali or alkaline metal hydroxides, carbonates, bicarbonates, alkoxides; wherein inorganic base is preferably sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate; wherein inorganic base is more preferably sodium hydroxide, more preferably 50% aqueous sodium hydroxide. The reaction mixture is heated 80-130° C. for about 5-10 hours, preferably at 100-110° C. for about 8 hours. After completion of the reaction, the reaction mixture is cooled to 0-15° C., preferably at 10-15° C. to isolate the pure compound of formula IV having major threo isomer NLT 85%.
[0039] The present invention delivers more pure compound of formula IV as the process parameters are set in the way which gives the good yield and purity as well.
Stage 3A:
[0040] The preferred embodiment of the present invention is to provide a novel one-pot process to prepare methylphenidate hydrochloride of formula I from compound of formula IV. The esterification can be performed by reacting formula IV with methanol in the presence of catalyst. The catalyst can be selected from sulfuric acid, hydrochloric acid or acetic acid and the like. Then after, in-situ generated methylphenidate free base is converted to corresponding hydrochloride salt by reacting with alcoholic hydrochloric acid.
[0041] More specifically, Compound of formula IV is treated with methanol at 25-30° C. temperature followed by cooling. The cooling temperature can be −5-10° C., preferably 0-5° C. The catalyst is added to the reaction mixture and stirred for a while at 10-15° C. and the temperature is raised to distill the methanol partially. Preferably the temperature can be raised up to reflux temperature. Further, according to batch size fresh methanol is added into the reaction mixture and further maintained at reflux temperature for sufficient time. Preferably the reaction is maintained 5-50 hours, more preferably 25-30 hours. After completion of distillation the thick slurry mass is cooled to 20-25° C. and water is added followed by further cooling at temperature 10-15° C. and stirred for 10-15 minutes. The pH is adjusted at 6-8 by using base. The base can be sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate or ammonia, preferably sodium hydroxide. The suitable solvent is added into the reaction mixture at temperature about 25-30° C. The solvent include dichloromethane, ethylaceate diethylether, diisopropylether, methylethylether, toluene or xylene or mixture thereof. Further pH is adjusted to 11.5-12.5 and the mixture is stirred for 30 minutes. The organic layer is separated and solvent is distilled out. After completion of distillation, suitable solvent is added into the oily mass (in-situ venerated methylphenidate free base) followed by charcoal treatment. The suitable solvent can be selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol or acetone and mixture thereof. The volume of the solvent used against formula IV can be 1-20 volumes, preferably 9-10 volumes. The reaction mixture is filtered and filtrate is cooled to 5-10° C. Alcoholic hydrochloric acid is added into the reaction mixture and stirred for a while at 5-10° C. An alcoholic hydrochloric acid, wherein alcohol can be selected from methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol and the like. The reaction mixture is heated at 40-120° C., preferably 50-55° C. for 10-15 minutes and subsequently cooled to 5-10° C. The reaction mixture is then maintained for 30 minutes, filtered, washed and dried to get more than 99.7% pure methylphenidate hydrochloride of formula I.
[0042] The main advantage of this stage is to provide the product via one-pot synthesis. A one-pot synthesis is a strategy to improve the efficiency of a chemical reaction whereby a reactant is subjected to successive chemical reactions in just one reactor. This is much desired by chemists because avoiding a lengthy separation process, purification of the intermediate compounds and avoid drying step would save time and resources while increasing yield. The greatest advantage of this method is that fewer synthetic and isolation steps are employed as compared to the multi-step approach reported into the prior art.
Stage 3B:
[0043] As per the observations of scientists of the present invention is that the use of 9-10 volumes of the solvent gives higher quality as compared to use of 2-3 volumes of solvent at particular stage. The difference is broadly described as shown in below table.
[0044] The volumes of solvent (i.e methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol or acetone and mixture thereof) added into oily mass of methylphenidate free base obtained from stage 3A, are preferably 2-3 volumes.
[0045] In other words, after distillation of the solvent (i.e dichloromethane, ethylaceate diethylether, diisopropylether, methylethylether, toluene or xylene or mixture thereof) described in stage 3A, the obtained oily mass of methylphenidate free base is treated with different solvent volumes and gives different purity results as described in below table. Hence stage 3B may need purification to remove unwanted isomer and impurities.
[0000]
Stage 3A
Stage 3B
Solvent
Isopropanol
Isopropanol
Solvent Volume
9-10
2-3
HPLC Purity
~99.8%
~99.3%
Stage 4B:
[0046] Methylphenidate hydrochloride of formula I from stage—3B is purified by treating with suitable solvent. The suitable solvent includes methanol, ethanol, isopropanol, n-butanol, isobutanol, tert-butanol, acetone, acetonitrile or mixture thereof. The reaction temperature is ambient to reflux temperature, preferably up to 110-120° C. for a time sufficient. The reaction mixture is then cooled to 0-30° C., preferably 25-30° C. and maintained for 30 minutes followed by filtration at 25-30° C. The obtained cake is washed with solvent, dried to give more than 99.8% pure methylphenidate hydrochloride.
[0047] Hence the parameters set for the purification in present invention make the product pharmacopoeially acceptable worldwide.
[0048] The invention is further defined by reference to the following examples describing in detail by the preparation of the compounds of the invention. It will be apparent to those skilled in the art that many modifications, both to materials and methods, may be practiced without departing from the scope of the invention.
EXAMPLES
Stage—1: Preparation of 2-phenyl2-(piperidin-2-yl)acetamide
[0049] A solution of 2-phenyl-2-(pyridine2-yl) acetamide (200 g, 0.942 mole) it glacial acetic acid (1000 ml) was hydrogenated in the presence of palladium on carbon (20 gm) at 55-65° C. under 4.5 Kg/cm 2 of hydrogen for 15 hours. The reaction mixture was filtered through celite bed. The obtained filtrate was concentrated under vacuum below 80° C. and residue were dissolved in water (1400 ml) and treated with activated carbon. The reaction mixture filtered through celite bed. The pH 12 was adjusted with aqueous sodium hydroxide. The precipitated free base was washed with water and the product dried in tray dryer at 70° C. to give 180 g of product of racemic mixture of erythro- and threo-2-phenyl-2-(piperidine-2-yl) acetamide as a white solid having HPLC purity: Erythro content: NMT 80% Threo content: NLT 20%.
Stage—2: Preparation of threo-2-phenyl-2-(piperidin-2-yl) acetamide
[0050] Racemic mixture of erythro- and threo-2-phenyl-2-(piperidine-2-yl) acetamide (100 gm) was treated with 50% aqueous sodium hydroxide (600 gm). The reaction mixture was heated at 100-110° C. for 8 hours under stirring followed by cooling at 10-15° C. The obtained material was filtered and wet cake was given water (300 ml×3) slurry. Dried the cake at 60-70° C. to give 90 gm titled compound having HPLC purity: Threo content: NLT 85%, Erythro content: NMT 15%.
Stage—3A [Method 1]: Preparation of Methylphenidate Hydrochloride from threo-2-phenyl-2-piperidyl acetamide [Threo isomer NLT 85%]
[0051] In methanol (800 ml), threo-2-phenyl-2-(piperidin-2-yl) acetamide (200 gm) was added at ambient temperature. The reaction mixture was cooled to 0-5° C. followed by addition of sulfuric acid (359 gm) drop wise within 45-60 minutes. The mass was stirred for 10-15 minutes at 10-15° C. and temperature was then raised up to 25-30° C. The reaction mass was heated at temperature 75-80° C. within 45-60 minutes and maintained at reflux for 20 hours to distill 2 volume of methanol. Fresh 2 volume of methanol was added into the reaction mass. Further it is maintained at reflux for 8 hours. After completion of reaction, methanol was distilled out at 75-80° C. and degassed under vacuum. The thick residue was cooled to 20-25° C. and water (2800 ml) was added. Cooled the mass up to 10-15° C. and stirred for 10 minutes followed by adjusting pH at 6-8 by adding caustic soda. Into the reaction mixture dichloromethane (600 ml) was added at 25-30° C. and pH was adjusted to 11.5-12.5. The mixture was then stirred for 30 minutes at 25-30° C. The organic layer was separated. Again dichloromethane (200ml×2) was added to aqueous layer and separated. Combined the organic layers. Dichloromethane is distilled out at temperature 45-50° C. and degassed under vacuum. After completion of distillation, isopropanol (2000 ml) added into the oily mass followed by charcoal treatment. The reaction mixture was filtered and washed with isopropanol (200 ml). The filtrate was then cooled up to 5-10° C. Isopropanolic hydrochloric acid (190 gm) was added to the reaction mass followed by stirring for 30 minutes at 5-10° C. The reaction mixture was heated at 50-55° C. for 10-15 minutes followed by cooling at 5-10° C. The reaction mass was maintained at 5-10° C. for 30 minutes. Filtered the mass at 5-10° C. and washed with isopropanol (200 ml). The wet cake was dried at 70-75° C. to get methylphenidate hydrochloride (170 gm) having HPLC purity: Threo content: 99.8%, Erythro content: 0.1%.
Stage—3B [Method 2]: Preparation of Methylphenidate Hydrochloride from threo-2-phenyl-2-piperidyl acetamide [Threo isomer NLT 85%1]
[0052] In methanol (800 ml), threo-2-phenyl-2-(piperidin-2-yl) acetamide (200 gm) was added at ambient temperature. The reaction mixture was cooled to 0-5° C. followed by addition of sulfuric acid (359 gm) drop wise within 45-60 minutes. The mass was stirred for 10-15 minutes at 10-15° C. and temperature was then raised up to 25-30° C. The reaction mass was heated at temperature 75-80° C. Within 45-60 minutes and maintained at reflux for 20 hours to distill 2 volume of methanol. Fresh 2 volume of methanol was added into the reaction mass. Further it is maintained at reflux for 8 hours. After completion of reaction, methanol was distilled out at 75-80° C. and degassed under vacuum. The thick residue was cooled to 20-25° C. and water (2800 ml) was added. Cooled the mass up to 10-15° C. and stirred for 10 minutes followed by adjusting pH at 6-8 by adding caustic soda. Into the reaction mixture dichloromethane (600 ml) was added at 25-30° C. and pH was adjusted to 11.5-12.5. The mixture was stirred for 30 minutes at 25-30° C. The organic layer was separated. Again dichloromethane (200ml×2) was added to aqueous layer and separated. Combined the organic layers. Dichloromethane is distilled out at temperature 45-50° C. and degassed under vacuum. After completion of distillation, isopropanol (400 ml) was added to the reaction mass followed by charcoal treatment. Filtered the reaction mass, cooled up to 5-10° C. and isopropanolic hydrochloric acid (190 gm) was added into it. Stirred the mass for 30 minutes at 5-10° C. The reaction mass was heated at 50-55° C. and maintained for 10-15 minutes followed by cooling at 5-10° C. The reaction mass was maintained at 5-10° C. for 1 hour. Filtered the mass at 5-10° C. and washed with isopropanol (200 ml). The wet cake was dried at 70-75° C. to get crude 190 gm methylphenidate hydrochloride having HPLC purity: Threo content: 99.32% Erythro content: 0.5%.
Stage—4B: Purification of crude Methylphenidate hydrochloride
[0053] Crude Methylphenidate hydrochloride (190 gm) from stage—3B [Method 2] was added into the n-butanol (874 ml) at temperature 25-30° C. The reaction mass was heated up to 110-120° C. and maintained for 10-15 minutes. The mass was then cooled to 25-30° C. within 2-3 hours and maintained for 30 minutes followed by filtration at 25-30° C. The obtained cake was washed with n-butanol (190 ml) and dried at 75-80° C. under vacuum to get pure 168 gm pure methylphenidate hydrochloride having HPLC purity: Threo content: 99.90%, Erythro content: 0.05%.
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The present invention relates to an industrially feasible and economically viable process for the preparation of methylphenidate hydrochloride of formula I and its intermediates thereof.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application 61/359,846 filed on Jun. 30, 2010, the contents of which are incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The invention relates to a process for preparing tri-n-propylamine (TPA).
BACKGROUND
[0003] Tri-n-propylamine (TPA) is, inter alia, an important intermediate for the production of dyes, catalysts and corrosion inhibitors and for use in the pharmaceutical and cosmetics industry (cf., for example, BASF Technical Data Sheet, “Tripropylamine”).
[0004] In the amination of n-propanol by means of ammonia, a product mixture of mono-n-propylamine (MPA), di-n-propylamine (DPA) and tri-n-propylamine (TPA) is always obtained. The composition of the amine product mixture formed can largely be controlled via the process parameters in the reaction of propanol. However, the proportion of di-n-propylamine, in particular, in the product mixture is difficult to influence and it is often impossible to produce exactly the amine product mixture wanted by the market.
[0005] One possible way of controlling the amine product mixture would be the separate conversion of dialkylamine into trialkylamine by reaction with n-propanol. However, this possibility is not preferred for process engineering and chemical reasons [risk of runaway reactions (uncontrolled temperature rise), safety aspect].
[0006] It is known from NL 65644 and the equivalent U.S. Pat. No. 2,574,693 (Shell Dev. Comp.) that monobutylamine can be converted into dibutylamine over an Al 2 O 3 catalyst in the presence of ammonia at high temperatures.
[0007] CN1,325,842 A (Chinese Petro. Chem. Group) teaches the conversion of monoisopropylamine into diisopropylamine over a K/H-beta-zeolite at elevated temperature.
BRIEF SUMMARY
[0008] It was an object of the present invention to overcome the disadvantages of the prior art and provide an improved economical process for preparing tri-n-propylamine (TPA). The production process should give tri-n-propylamine in high yield, space-time yield (STY) and selectivity and also be particularly simple and economical.
[0009] It was recognized according to the invention that the di-n-propylamine formed, for example, by prior amination of n-propanol can be converted into tri-n-propylamine by a reaction (scrambling) of di-n-propylamine, optionally in the presence of ammonia, preferably in the absence of ammonia, and the n-propylamine product mix of a preceding n-propylamine synthesis can therefore be altered in a targeted manner in favor of the tertiary amine.
[0010] We have accordingly found a process for preparing tri-n-propylamine, in which di-n-propylamine is reacted in the presence of hydrogen and a copper-comprising heterogeneous catalyst. The reaction of DPA proceeds according to the scheme
[0000] di-n-propylamine--->tri-n-propylamine+NH 3
[0011] Small amounts of mono-n-propylamine are obtained as by-product.
[0012] In the disproportionation, di-n-propylamine is reacted over a copper-comprising heterogeneous catalyst. Preferably elevated pressure, preferably elevated temperature and the presence of hydrogen are the typical reaction conditions.
[0013] The reaction is preferably carried out an absolute pressure in the range from 20 to 150 bar, in particular from 40 to 150 bar, more particularly from 60 to 150 bar.
[0014] The reaction is preferably carried out at a temperature in the range from 180 to 260° C., in particular from 190 to 260° C., more particularly from 200 to 260° C.
[0015] The space velocity over the catalyst is preferably in the range from 0.3 to 3 kg/l·h, in particular from 0.3 to 0.7 kg/l·h, more particularly from 0.4 to 0.7 kg/l·h [kg of DPA/(liters of catalyst·hour)].
(Liters of Catalyst=Catalyst Bed Volume)
[0016] The amount of hydrogen used is preferably in the range from 200 to 2000 standard l/l·h, in particular from 250 to 700 standard l/l·h, more particularly from 300 to 600 standard l/l·h [standard liters (liters of catalyst·hour)]
[0000] (standard l=standard liters=volume under standard conditions (20° C., 1 bar absolute).
[0017] The process can be carried out continuously or batchwise. Preference is given to a continuous process.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Illustrative embodiments of the present invention are described herein with reference to the accompanying drawings, in which:
[0019] FIG. 1 is a schematic diagram depicting one embodiment of the integrated process for preparing tri-n-propylamine (TPA).
[0020] FIG. 2 is a schematic diagram depicting another embodiment of the integrated process for preparing tri-n-propylamine (TPA).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] For the synthesis, the starting material (DPA) is preferably heated in a stream of hydrogen and fed into the reactor. Hydrogen is preferably circulated in a gas recycle mode.
[0022] The starting material (DPA) can optionally be recirculated from a distillation column in which the reaction product mixture has been fractionated.
[0023] The starting material (DPA) can also be heated as an aqueous solution and passed to the catalyst bed, preferably with the gas recycle stream.
[0024] Preferred reactors are tube reactors. Examples of suitable reactors having a gas recycle stream may be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., vol. B 4, pages 199-238, “Fixed-Bed Reactors”.
[0025] As an alternative, the reaction is advantageously carried out in a shell-and-tube reactor or in a monostream plant.
[0026] In a monostream plant, the tube reactor in which the reaction is carried out can comprise a plurality of, (e.g. two or three) individual tube reactors connected in series. Optionally, intermediate introduction of feed (comprising the starting material DPA and/or H 2 ) and/or recycle gas and/or reactor output from a downstream reactor is advantageously possible here.
[0027] The heterogeneous catalyst used in the process of the invention comprises Cu and/or Ni and/or Co, preferably Cu and Ni and/or Co, particularly preferably Cu and Ni and Co.
[0028] The heterogeneous catalyst preferably comprises an oxidic support material for the active metals, preferably aluminum oxide (gamma, delta, theta, alpha, kappa, chi or mixtures thereof) and/or zirconium dioxide (preferably monoclinic, tetragonal or cubic modification). A particularly preferred support material is aluminum oxide, in particular gamma-aluminum oxide.
[0029] In the process of the invention, the catalysts are preferably used in the form of catalysts which consist only of catalytically active composition and optionally a shaping aid (e.g. graphite or stearic acid) if the catalyst is used as shaped bodies, i.e. do not comprise further catalytically active constituents.
[0030] In this context, the oxidic support material aluminum oxide (Al 2 O 3 ), zirconium dioxide (ZrO 2 ) are considered to be part of the catalytically active composition.
[0031] The catalysts are used by introducing the catalytically active composition which has been milled to powder into the reaction vessel or by milling the catalytically active composition, mixing it with shaping aids, shaping and heat treatment to give shaped catalyst bodies, for example pellets, spheres, rings, extrudates (e.g. rods), and arranging the shaped catalyst bodies in the reactor.
[0032] The concentrations indicated (in % by weight) for the components of the catalyst are in each case, unless indicated otherwise, based on the catalytically active composition of the finished catalyst after its last heat treatment and before reduction with hydrogen.
[0033] The catalytically active mass of the catalyst after its last heat treatment and before reduction with hydrogen is defined as the sum of the masses of the catalytically active constituents and the abovementioned catalyst support materials and comprises essentially the following constituents:
[0000] aluminum oxide (Al 2 O 3 ) and/or zirconium dioxide (ZrO 2 ) and oxygen-comprising compounds of copper and/or of nickel and/or of cobalt.
[0034] The sum of the abovementioned constituents of the catalytically active composition is usually from 70 to 100% by weight, preferably from 80 to 100% by weight, particularly preferably from 90 to 100% by weight, in particular >95% by weight, very particularly >98% by weight, more particularly >99% by weight, e.g. particularly preferably 100% by weight.
[0035] The catalytically active composition of the catalysts according to the invention and catalysts used in the process of the invention can further comprise one or more elements (oxidation state 0) or inorganic or organic compounds thereof selected from groups I A to VI A and I B to VII B and VIII of the Periodic Table.
[0036] Examples of such elements and compounds thereof are:
[0000] transition metals such as Mn and MnO 2 , Mo and MoO 3 , W and tungsten oxides, Ta and tantalum oxides, Nb and niobium oxides or niobium oxalate, V and vanadium oxides and vanadyl pyrophosphate; lanthanides such as Ce and CeO 2 or Pr and Pr 2 O 3 ; alkaline earth metal oxides such as SrO; alkaline earth metal carbonates such as MgCO 3 , CaCO 3 and BaCO 3 ; alkali metal oxides such as Na 2 O, K 2 O; alkali metal carbonates such as Li 2 CO 3 , Na 2 CO 3 and K 2 CO 3 ; boron oxide (B 2 O 3 ).
[0037] The catalytically active composition of the catalyst used in the process of the invention preferably comprises no rhenium, no ruthenium, no iron and/or no zinc, in each case neither in metallic (oxidation state=0) form nor in an ionic (oxidation state≠0), in particular oxidized, form.
[0038] The catalytically active composition of the catalyst used in the process of the invention preferably comprises no silver and/or molybdenum, in each case neither in metallic (oxidation state=0) form nor in an ionic (oxidation state≠0), in particular oxidized, form.
[0039] The catalytically active composition of the catalyst preferably comprises no oxygen-comprising compounds of silicon and/or of chromium.
[0040] The catalysts can be produced by known methods, e.g. by precipitation, precipitation onto a support, impregnation.
[0041] The catalytically active composition of preferred heterogeneous catalysts before treatment with hydrogen comprises
[0000] from 20 to 85% by weight, preferably from 20 to 65% by weight, particularly preferably from 22 to 40% by weight, of oxygen-comprising compounds of zirconium, calculated as ZrO 2 ,
from 1 to 30% by weight, particularly preferably from 2 to 25% by weight, of oxygen-comprising compounds of copper, calculated as CuO,
from 14 to 70% by weight, preferably from 15 to 50% by weight, particularly preferably from 21 to 45% by weight, of oxygen-comprising compounds of nickel, calculated as NiO, with the molar ratio of nickel to copper, preferably being greater than 1, in particular greater than 1.2, very particularly preferably from 1.8 to 85, and
from 0 to 5% by weight, in particular from 0.1 to 3% by weight, of oxygen-comprising compounds of molybdenum, calculated as MoO 3 .
[0042] In a further variant, the catalytically active composition of these preferred catalysts before treatment with hydrogen additionally comprises
[0000] from 15 to 50% by weight, particularly preferably from 21 to 45% by weight, of oxygen-comprising compounds of cobalt, calculated as CoO.
[0043] The oxygen-comprising compounds of copper, nickel and optionally cobalt, in each case calculated as CuO, NiO and CoO, of the preferred catalysts are generally comprised in total amounts of from 15 to 80% by weight, preferably from 35 to 80% by weight, particularly preferably from 60 to 78% by weight, in the catalytically active composition (before treatment with hydrogen), with the molar ratio of nickel to copper particularly preferably being greater than 1.
[0044] The catalytically active composition of particularly preferred heterogeneous catalysts before treatment with hydrogen comprises
[0000] from 20 to 90% by weight, preferably from 40 to 85% by weight, particularly preferably from 60 to 80% by weight, of oxygen-comprising compounds of aluminum, calculated as Al 2 O 3 ,
from 1 to 30% by weight, preferably from 2 to 25% by weight, particularly preferably from 3 to 20% by weight, of oxygen-comprising compounds of copper, calculated as CuO,
from 1 to 40% by weight, preferably from 3 to 30% by weight, particularly preferably from 5 to 20% by weight, of oxygen-comprising compounds of nickel, calculated as NiO, with the molar ratio of nickel to copper particularly preferably being greater than 1, preferably greater than 1.2, particularly preferably from 1.8 to 8.5, and
from 1 to 40% by weight, preferably from 3 to 30% by weight, particularly preferably from 5 to 20% by weight, of oxygen-comprising compounds of cobalt, calculated as CoO.
[0045] The oxygen-comprising compounds of nickel, cobalt and copper, in each case calculated as NiO, CoO and CuO, are preferably comprised in total amounts of from 10 to 80% by weight, particularly preferably from 15 to 60% by weight, very particularly preferably from 20 to 40% by weight, in the catalytically active composition (before treatment with hydrogen), with the molar ratio of nickel to copper particularly preferably being greater than 1.
[0046] Further preferred heterogeneous catalysts in the process of the invention are
[0000] catalysts which are disclosed in DE 19 53 263 A (BASF AG) and comprise cobalt, nickel and copper and aluminum oxide and/or silicon dioxide and have a metal content of from 5 to 80% by weight, in particular from 10 to 30% by weight, based on the total catalyst, where the catalysts comprise, calculated on the basis of the metal content, from 70 to 95% by weight of a mixture of cobalt and nickel and from 5 to 30% by weight of copper and the weight ratio of cobalt to nickel is from 4:1 to 1:4, in particular from 2:1 to 1:2, for example the catalyst having the composition 10% by weight of CoO, 10% by weight of NiO and 4% by weight of CuO on Al 2 O 3 used in the examples there,
catalysts which are disclosed in EP 382 049 A (BASF AG) or catalysts which can be produced correspondingly and whose catalytically active composition before treatment with hydrogen comprises
from 20 to 85% by weight, preferably from 70 to 80% by weight, of ZrO 2 and/or Al 2 O 3 ,
from 1 to 30% by weight, preferably from 1 to 10% by weight, of CuO,
and from 1 to 40% by weight, preferably from 5 to 20% by weight, of each of CoO and NiO, for example the catalysts described in loc. cit. on page 6 which have the composition 76% by weight of Zr, calculated as ZrO2, 4% by weight of Cu, calculated as CuO, 10% by weight of Co, calculated as CoO, and 10% by weight of Ni, calculated as NiO,
catalysts which are disclosed in EP 963 975 A (BASF AG) and whose catalytically active composition before treatment with hydrogen comprises
from 22 to 40% by weight of ZrO 2 ,
from 1 to 30% by weight of oxygen-comprising compounds of copper, calculated as CuO,
from 15 to 50% by weight of oxygen-comprising compounds of nickel, calculated as NiO, with
the molar ratio of Ni:Cu being greater than 1,
from 15 to 50% by weight of oxygen-comprising compounds of cobalt, calculated as CoO,
from 0 to 10% by weight of oxygen-comprising compounds of aluminum and/or manganese,
calculated as Al 2 O 3 or MnO 2 ,
and no oxygen-comprising compounds of molybdenum,
for example the catalyst A which is disclosed in loc. cit., page 17, and has the composition 33% by weight of Zr, calculated as ZrO2, 28% by weight of Ni, calculated as NiO, 11% by weight of Cu, calculated as CuO, and 28% by weight of Co, calculated as CoO,
catalysts which are disclosed in EP 696 572 A (BASF AG) and whose catalytically active composition before reduction with hydrogen comprises from 20 to 85% by weight of ZrO 2 , from 1 to 30% by weight of oxygen-comprising compounds of copper, calculated as CuO, from 30 to 70% by weight of oxygen-comprising compounds of nickel, calculated as NiO, from 0.1 to 5% by weight of oxygen-comprising compounds of molybdenum, calculated as MoO 3 , and from 0 to 10% by weight of oxygen-comprising compounds of aluminum and/or manganese, calculated as Al 2 O 3 or MnO 2 , for example the catalyst which is disclosed in loc. cit., page 8, and has the composition 31.5% by weight of ZrO2, 50% by weight of NiO, 17% by weight of CuO and 1.5% by weight of MoO 3 ,
catalysts which are described in EP 1 270 543 A1 (BASF AG) and comprise at least one element or compound of an element of groups VIII and IB of the Periodic Table,
and
catalysts which are described in EP 1 431 273 A (BASF AG) and in the production of which a precipitation of catalytically active components onto monoclinic, tetragonal or cubic zirconium dioxide has been carried out.
[0047] The catalysts produced can be stored as such. Before use as catalysts in the process of the invention, they are prereduced by treatment with hydrogen (=activation of the catalyst). However, they can also be used without prereduction, in which case they are then reduced (=activated) by the hydrogen present in the reactor under the conditions of the process of the invention.
[0048] To activate the catalyst, it is preferably exposed to a hydrogen-comprising atmosphere or a hydrogen atmosphere at a temperature in the range from 100 to 500° C., in particular from 150 to 400° C., very particularly preferably from 180 to 300° C., for a period of at least 25 minutes, in particular at least 60 minutes. The time for which the catalyst is activated can be up to 1 h, particularly preferably up to 12 h, in particular up to 24 h.
[0049] During this activation, at least part of the oxygen-comprising metal compounds present in the catalysts is reduced to the corresponding metals, so that these are present together with the various oxygen compounds in the active form of the catalyst.
[0050] According to the invention, the process of the invention is, in particular, carried out for preparing TPA by the above-described disproportionation of di-n-propylamine in an integrated process in which tri-n-propylamine (TPA), in particular, is prepared selectively as described below. The integrated process allows precise control of the proportions in the amine product mixture of mono-n-propylamine (MPA), di-n-propylamine (DPA) and tri-n-propylamine (TPA). This high product flexibility advantageously enables the product mix wanted by the market to be prepared precisely.
[0051] See FIGS. 1 and 2 for preferred embodiments.
[0052] An amination of n-propanol takes place, preferably continuously, in a main reactor. For this purpose, n-propanol (PrOH) is reacted with ammonia over an amination catalyst and optionally in the presence of hydrogen to give a mixture of mono-n-propylamine, di-n-propylamine and tri-n-propylamine. The reaction of n-propanol with ammonia in the main reactor (reactor 1), which can naturally also be divided into two or more reactors connected in series or in parallel, can be carried out by processes known to those skilled in the art (see, for example, Kirk-Othmer Encyclopedia of Chemical Technology, vol. 2, pages 537-553).
[0053] Ammonia, n-propanol and optionally hydrogen are separated off from the reaction product mixture and of these at least ammonia and propanol are recirculated to the reactor. In addition, mono-n-propylamine, di-n-propylamine and tri-n-propylamine are separated by distillation, e.g. in a cascade of distillation columns.
[0054] Di-n-propylamine which has been separated off is fed into a reactor (converting reactor) in which, according to the invention, the reaction to form TPA occurs, preferably continuously, in the presence of a copper-comprising heterogeneous catalyst.
[0055] The output from the converting reactor is fed to the abovementioned work-up section for the reaction product mixture from the main reactor.
[0056] Such an integrated mode of operation allows tri-n-propylamine to be prepared from n-propanol with high selectivity, e.g. in the range from 40 to 99% (based on n-propanol).
[0057] Particular and preferred embodiments of the process are as follows:
[0058] The reaction of n-propanol with ammonia is carried out in a reactor (reactor 1), preferably over a transition metal catalyst, e.g. a copper- and/or nickel-comprising catalyst, at generally from 1 to 220 bar and generally from 130 to 250° C., or over an acid catalyst, e.g. a metal oxide or zeolite at generally from 1 to 36 bar and generally from 300 to 500° C.
[0059] The catalyst is preferably arranged as a fixed bed in the reactor (reactor 1).
[0060] The propanol conversion is generally maintained at >90%, preferably >95%.
[0061] To maintain the catalyst activity, hydrogen is preferably also fed into the reactor (reactor 1) when metal catalysts are used.
[0062] The output from the reactor for the n-propanol reaction (reactor 1) is subsequently depressurized to preferably from 20 to 30 bar. Any “low-pressure hydrogen” obtained, which may still comprise some ammonia, can be compressed and circulated via the reactor for the n-propanol reaction (reactor 1) and/or can, optionally after compression, be used directly (or after removal of ammonia comprised therein by means of a gas scrub) as feed for the reactor for the DPA reaction (reactor 2) (see below).
[0063] The reaction product mixture remaining after the hydrogen has been separated off, which comprises essentially or consists of ammonia, water, n-propanol, MPA, DPA and TPA, is separated into the individual constituents according to the different vapor pressures. The multistage separation into the constituents is preferably carried by distillation, in particular by continuous distillation, and/or by liquid-liquid phase separation, in particular by continuous liquid-liquid phase separation. Such separation processes are known to those skilled in the art, e.g. from Kirk-Othmer Encyclopedia of Chemical Technology.
[0064] The distillation columns required for obtaining the individual products, especially the desired propylamines, in pure form by distillation can be designed by a person skilled in the art using familiar methods (e.g. number of theoretical plates, reflux ratio, etc.).
[0065] The separation of the reaction product mixture resulting from the reactor for the n-propanol reaction (reactor 1) is particularly preferably carried out in two separation sequences by multistage distillation, with ammonia and any hydrogen present firstly being separated off in the first separation sequence (separation sequence 1) and a separation into n-propanol, MPA, DPA, TPA, water and secondary components (SC) being carried out in the second separation sequence (separation sequence 2).
[0066] Any n-propanol obtained as a result of incomplete reaction in this separation of the reaction product mixture resulting from the reactor for the n-propanol reaction (reactor 1) is preferably recirculated to the reactor (reactor 1).
[0067] The dipropylamine (DPA) obtained in this separation is, optionally after branching off a partial amount into a storage tank, fed into a separate reactor (converting reactor, reactor 2) for conversion into tri-n-propylamine (TPA) in the presence of a copper-comprising heterogeneous catalyst.
[0068] The disproportionation of DPA to form TPA in the separate reactor (reactor 2), which can naturally also be divided into two or more reactors connected in series or in parallel, is carried out according to the above-described process.
[0069] To maintain the catalyst activity, hydrogen is fed into the reactor (reactor 2).
[0070] The ammonia- and hydrogen-comprising reaction product mixture from the separate conversion of DPA into TPA is, in an embodiment of the integrated process of the invention (variant 1), combined with the output from the reactor for the n-propanol reaction (reactor 1) and the two are worked up together, i.e. fed to the separation of the reaction product mixture resulting from the reactor for the n-propanol reaction (reactor 1), in particular to the first separation sequence (separation sequence 1) of the separation of the reaction product mixture resulting from the reactor for the n-propanol reaction (reactor 1).
[0071] A process scheme of this variant 1 of the integrated process of the invention is shown in the appendix ( FIG. 1 ).
[0072] In a further embodiment of the integrated process of the invention (variant 2), hydrogen and ammonia are firstly separated off (separation sequence 3) from the reaction product mixture from the separate conversion of DPA into TPA and are preferably each recirculated (ammonia to the reactor for the n-propanol reaction (reactor 1), hydrogen to the reactor for the n-propanol reactor (reactor 1) and/or the reactor for the DPA reaction (reactor 2)) and the remaining reaction product mixture comprising n-propylamines is then fed to the second separation sequence (separation sequence 2) of the separation of the reaction product mixture resulting from the reactor for the n-propanol reaction (reactor 1).
[0073] A process scheme of this variant 2 of the integrated process of the invention is shown in the appendix ( FIG. 2 ).
[0074] The integration of the disproportionation stage into a conventional n-propylamine production process based on n-propanol enables the outputs from the two reactions to be advantageously worked up together.
[0075] Liberated ammonia obtained in the work-up can be recirculated to the amination of n-propanol (reactor 1) and hydrogen obtained in the work-up can be recirculated to the converting reactor (reactor 2) and/or to the amination of n-propanol (reactor 1).
[0076] All pressures indicated are absolute pressures.
EXAMPLES
Catalyst “A S4”
[0077] The catalyst “A S4”, a Cu/Co/Ni/gamma-Al 2 O 3 catalyst as disclosed in DE 19 53 263 A (BASF AG), was produced by impregnation of 4 mm extrudates.
[0078] The catalyst had the following composition before treatment (activation) with hydrogen:
[0000] 10% by weight of CoO, 10% by weight of NiO and 4% by weight of CuO on gamma-Al 2 O 3 .
Example 1
[0079] The starting material 100% DPA was disproportionated continuously in the absence of NH 3 over the catalyst “A S4”. At a pressure of 140 bar, a space velocity of 0.50 kg/·h and an amount of hydrogen of 500 standard l/l·h, the following composition of the reaction product mixture (in % by weight) was obtained at 250° C.: 4% of MPA, 51% of DPA and 45% of TPA.
Example 2
[0080] The starting material 100% DPA was disproportionated continuously in the absence of NH 3 over the catalyst “A S4”. At a pressure of 85 bar, a space velocity of 0.51 kg/l·h and an amount of hydrogen of 400 standard l/l·h, the following composition of the reaction product mixture (in % by weight) was obtained at 220° C.: 4% of MPA, 47% of DPA and 49% of TPA.
Example 3
[0081] The starting material 100% DPA was disproportionated continuously in the absence of NH 3 over the catalyst “A S4”. At a pressure of 40 bar, a space velocity of 0.59 kg/l·h and an amount of hydrogen of 405 standard l/l·h, the following composition of the reaction product mixture (in % by weight) was obtained at 215° C.: 5% of MPA, 50% of DPA and 45% of TPA.
Example 4
[0082] The starting material 100% DPA was disproportionated continuously in the absence of NH 3 over the catalyst “A S4”. At a pressure of 140 bar, a space velocity of 0.50 kg/l·h and an amount of hydrogen of 600 standard l/l·h, the following composition of the reaction product mixture (in % by weight) was obtained at 250° C.: 4% of MPA, 50% of DPA and 46% of TPA.
Example 5
[0083] The starting material 100% DPA was disproportionated continuously in the absence of NH 3 over the catalyst “A S4”. At a pressure of 40 bar, a space velocity of 3.00 kg/l·h and an amount of hydrogen of 200 standard l/l·h, the following composition of the reaction product mixture (in % by weight) was obtained at 240° C.: 6% of MPA, 51% of DPA and 43% of TPA.
Example 6
[0084] The starting material 100% DPA was disproportionated continuously in the absence of NH 3 over the catalyst “A S4”. At a pressure of 85 bar, a space velocity of 0.50 kg/l·h and an amount of hydrogen of 200 standard l/l·h, the following composition of the reaction product mixture (in % by weight) was obtained at 200° C.: 4% of MPA, 57% of DPA and 39% of TPA.
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Process for preparing tri-n-propylamine (TPA), wherein di-n-propylamine (DPA) is reacted in the presence of hydrogen and a copper-comprising heterogeneous catalyst.
An integrated process for preparing TPA, which comprises the following operations:
I) reaction of n-propanol with ammonia in a reactor in the presence of an amination catalyst and optionally hydrogen to form a mixture of mono-n-propylamine, DPA and TPA, II) separation of unreacted ammonia, unreacted n-propanol and possibly hydrogen from the reaction product mixture and recirculation of at least the ammonia and propanol to the reactor in I) and also separation of the n-propylamine mixture by distillation and isolation of the TPA, III) reaction of the DPA obtained in the separation by distillation in II) in a reactor in the presence of hydrogen and a copper-comprising heterogeneous catalyst to form TPA and IV) feeding of the reactor output from III) to operation II).
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CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application No. 61/591,488 titled “Disposal of Sulfur Through Use as Sand-Sulfur Mortar,” filed on Jan. 27, 2012, the disclosure of which is incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a composition and method for disposing of sulfur by converting waste sulfur to a useful product, namely, by producing a sulfur based mortar.
[0004] 2. Description of the Related Art
[0005] Typical cement concrete is a mixture of Portland cement, sand, aggregates, and water. Such Portland cement concrete can be used for a variety of purposes including the construction of buildings. The Portland cement is the binder that binds the concrete together. Unfortunately, the production of Portland cement is energy intensive because production consumes significant energy and, thus, produces considerable carbon dioxide (CO 2 ). Indeed, the production of Portland cement includes heating cement clinker to 1400-1500 C, in a rotating kiln. In addition to the environmental issues, the heat required to produce cement clinker is a health and safety risk. Such energy consumption during production causes concerns about using it as a building material. Sulfur, which is abundantly produced by oil refineries, can be used as an alternative binder in concrete.
[0006] Conventional sulfur concrete contains amounts of sulfur (as a binder), aggregates, sand, and fly ash. Fly ash, which is a waste product from the combustion of coal at thermal power plants, is used as a filler material, Fly ash, however, is not always readily available. Furthermore, fly ash can be relatively expensive because of demand for fly ash for use in Portland cement concrete. The cost and unavailability of fly ash discourages the use of sulfur concrete in building components.
[0007] There are other disadvantages to the use of conventional sulfur concrete. For example, polymer modifiers are typically needed as a modifier to increase the ductility of sulfur concrete, but such modifiers significantly increase the cost of sulfur concrete. Another disadvantage is that sulfur concrete prepared with conventional aggregate, such as gravel and rock, shows signs of deterioration when exposed to water and sulfuric acid. Therefore, it would be beneficial to have a sulfur concrete that eliminates the use of fly ash and polymer modifiers.
SUMMARY OF THE INVENTION
[0008] Embodiments of the present invention include a sulfur-sand limestone mortar, a method of preparing the sulfur-sand limestone mortar, and a method for disposing of elemental sulfur. Specifically, embodiments include a sulfur concrete mix incorporating sand that utilizes limestone powder. An embodiment of the mixture includes about 72.5% sand, 17.5% sulfiir, and 10% limestone powder as filler. Experimental data shows that embodiments of the sulfur-sand limestone mortar exhibit good performance when exposed to water and sulfuric acid. The properties of embodiments of the sulfur-sand limestone mortar are comparable or better than those of sand-cement mortar and sulfur mix with fly ash. Furthermore, limestone powder can be more readily available and less expensive than fly ash.
[0009] Embodiments of the sulfur-sand limestone mortar can be used for preparing structural components, such as, for example, pavement slabs and tiles for flooring purposes. Also, embodiments of the sulfur-sand limestone mortar can be used as an acid-resistant flooring and fair coat. Furthermore, sulfur is a by-product of oil production that must be disposed of. In embodiments, sulfur-sand limestone mortar can be used as a method to dispose of sulfur in an environmentally friendly manner.
[0010] In embodiments, a sulfur mortar composition includes elemental sulfur; limestone powder; and sand; the elemental sulfur being heated to a liquid state and the limestone powder and the sand each being heated to at least 140 C and then combined to create a liquid state mortar composition, and then the elemental sulfur solidifying as it cools to create a solid state mortar composition.
[0011] In embodiments, at least a portion of the limestone powder has a fineness that allows it to pass through No. 100 sieve. In embodiments, the composition can include, by weight, about 70-75% sand. In embodiments, the composition can include, by weight, about 15-20% elemental sulfur. In embodiments, the composition can include, by weight, about 10-15% limestone powder. In embodiments, the composition can include, by weight, about 70-75% sand, 15-20% elemental sulfur, and 10-15% limestone powder. In embodiments, the composition can include, by weight, about 72.5% sand, 17.5% elemental sulfur, and 10% limestone powder.
[0012] In embodiments, the composition can have an absence of fine entrained gas cells. In embodiments, the composition can have an absence of modifiers and, more specifically, embodiments can have an absence of platicizers. In its liquid state, the composition can have sufficient flowability to occupy formworks when it is poured. The composition, in the solid state, can be stable in water. When in the solid state, embodiments of the composition absorb less than 1% water by weight.
[0013] In embodiments of a method for producing a sulfa mortar composition, the method includes the steps of heating elemental sulfur to a liquid state, heating each of limestone powder and sand to at least 140 C, combining the liquid-state elemental sulfur with each of the heated limestone powder and sand to define a mortar mixture, and cooling the mortar mixture until it solidifies.
[0014] In embodiments of a method for disposing of elemental sulfur, method includes the steps of heating elemental sulfur to a liquid state, heating each of limestone powder and sand to at least 140 C, combining the liquid-state elemental sulfur with each of the heated limestone powder and sand to define a mortar mixture, and cooling the mortar mixture until it solidifies. The elemental sulfur can be obtained as a by-product of mineral production.
DETAILED DESCRIPTION OF THE INVENTION
[0015] Solid sulfur can be produced as a by-product of oil and gas production. As one of ordinary skill will appreciate, elemental sulfur (S°) is a molecule containing only sulfur atoms (as opposed to, for example, a sulfate, such as SO 4 ). Elemental sulfur can have a yellow color when in crystalline form. Elemental sulfur can be produced as a byproduct when sulfur contaminants are removed when refining petroleum and natural gas. The sulfur can melt at temperatures in the range of about 127° C. to about 149° C. (260° to 300° F.). In an embodiment of the present invention, elemental sulfur is disposed of through a process that includes heating the sulfur to a molten state and then combining it with limestone powder and sand. In one embodiment of the present invention, a sulfur-sand limestone mortar (“SSLM”) mix can include elemental sulfur, limestone powder, and sand.
[0016] Limestone powder is produced from limestone, such as by crushing limestone. Limestone can be a crystalline form of calcium carbonate (CaCO 3 ). The limestone powder is a fine powder having relatively uniform particle sizes or having various particles sizes. In one embodiment, the limestone powder can be finer than 150 micro meters, thus passing a No. 100 sieve. In one embodiment, the limestone powder improves the plasticity of the SSLM mixture, dilutes the sulfur concentration, and makes it less viscous. In one embodiment, the limestone powder can have the composition shown in Table 1.
[0000]
TABLE 1
Composition of Exemplary Embodiment of Limestone Powder
Constituent
Weight, %
CaO
45.7
SiO 2
11.8
Fe 2 O 3
0.68
Al 2 O 3
2.17
MgO
1.8
LOI
35.1
[0017] In one embodiment, the limestone powder does not impact the resistance of SSLM to water or acid, whereas limestone aggregates can have a negative impact. The limestone powder can act as a blender and finer. The limestone powder is also chemically bound with sulfur and therefore be protected from the fluids such as water and acid. Conventional limestone aggregate, in contrast, is directly exposed to the acid formed as a result of reaction between sulfur and water and, thus, be prone to attack by water. In various embodiments, the percentage of limestone powder can be limited to the range of about 10% to about 12.5%, as opposed to conventional sulfur concrete which can have about 47% limestone aggregate. For purposes of this specification, composition percentages indicate percentage by weight, unless otherwise indicated. Furthermore, limestone powders are less susceptible to soundness loss or loss on abrasion than the limestone aggregates. (Soundness loss test is applicable to samples retained on sieve no. 50 (300 micro meters) or larger and the loss on abrasion test is applicable to samples retained on number 8 sieve (2.36 mm) or larger).
[0018] Sand can be classified as rolled sand or dune sand. Dune sand is a type of wind-carried sand that has been piled up by the wind into a sand dune and can have rounded mineral grains. Dune sand or rolled sand can include mineral grains having diameters ranging from 0.1 to 1 mm. The sand can be used as fine aggregate in the SSLM. In one embodiment, the sand used as fine aggregate can be finer than 0.6 mm. In one embodiment, the fine aggregate can be quartz sand. The mineral grains can be quartz or other minerals.
[0019] In one embodiment, fine aggregate such as quartz sand is not vulnerable or is less vulnerable to damage due to, among other reasons, the fact that it is mostly quartz and finer than 0.6 mm. Acids have very low reaction on quartizitic material. Moreover, because the quartz sand is very fine, it can blend with the sulfur and limestone to form a dense matrix. The results are different if coarse sand or carbonate sand is used. Also, the carbonate-based sand, being alkaline in nature, could react with the acid formed due to the reaction of sulfur with water. Indeed, carbonate-based sand could react with the sulfuric acid produced by sulfur in the presence of moisture leading to cracking of specimens. The composition of sand for one embodiment of the SSLM is shown in Table 2.
[0000]
TABLE 2
Composition of Exemplary Embodiment of Fine Aggregate
Constituent
Weight, %
SiO 2
80-98
Fe 2 O 3
0.3-0.9
Al 2 O 3
0.6-4.0
MgO
0.3-1.0
CaO
0.2-7.0
[0020] The size gradation of sand for embodiments of the SSLM are shown in Table 3.
[0000]
TABLE 3
Size Gradation of Exemplary Embodiment of Fine Aggregate Sand
Sieve size (Nominal Opening, mm)
% passing
No 4 (4.75 mm)
100
No 8 (2.40 mm)
100
No 16 (1.20 mm)
100
No 30 (0.60 mm)
96.2
No 50 (0.30 mm)
61.4
No 100 (0.15 mm)
21.9
No 200 (0.075 mm)
1.0
[0021] The mixture created by combining molten sulfur, limestone powder, and sand can be used as a sulfur mortar. Sulfur concrete and sulfur mortar are each created by combining molten sulfur and one or more of aggregates, sand, and filler. The sulfur, once solidified, can serve as the binder in the sulfur concrete or sulfur mortar. The size of the aggregate can determine whether the composition is concrete or mortar, as mortar typically has small aggregate particles such as sand.
[0022] In one embodiment of the present invention, a sulfur-sand-limestone mortar (“SSLM”) mix can include elemental sulfur, sand, and limestone powder. Some embodiments do not use any polymer modifiers. The elemental sulfur can be, for example, the S 8 allotrope. Other allotropes of sulfur can be used, including S6, S7, S9-S15, S18, or S20. The sand can be quartz sand and can be dune sand or rolled sand. The limestone powder can be fine limestone powder such as, for example, finer than 150 micro meters (and thus passing a No. 100 sieve). The SSLM mix is prepared as a liquid by heating the elemental sulfur to at least 140 C to create a liquid state, and heating each of the limestone powder and the sand to at least 140 C. The liquid-state sulfur, the heated limestone powder, and the sand can then be combined such that the solids are suspended in the liquid sulfur. When the liquid sulfur cools, it can create a solid state SSLM.
[0023] One embodiment of sulfur-sand mortar can include about 70-75% sand, 15-20% sulfur, and 10-15% limestone powder. Some embodiments have an absence of modifiers. One embodiment can include 15-17.5% sulfur. One embodiment can include 82.5% dune sand. One embodiment can include 17.5% sulfur, 72.5% sand, 10% limestone powder, and an absence of polymer modifiers.
[0024] Each of the embodiments can have an absence of modifiers, such as chemical modifiers (including plasticizers, viscosotiers, and rheological modifiers) and air. in one embodiment, fine entrained gas cells are not intentionally introduced into the SSLM and, thus, the SSLM has an absence of fine entrained gas cells. This differs from state of the art methods which intentionally create fine entrained cells as a necessary step in creating sulfur concrete. Chemical modifiers are modifiers that are added to conventional sulfur mortar to alter the properties of the sulfur mortar. Examples of chemical modifiers that are used in conventional sulfur concrete, but not in embodiments of SSLM, can include dicyclopentadiene (DCPD); DCPD and an oligomer of cyclopentadiene; limonene; styrene; DCPD and styrene; naphthalene; olefinic hydrocarbon polymers; bitumen; 5-ethylidene-2-norbornene; and Chempruf™.
[0025] SSLM is more stable in moist and acidic environments than sulfur-sand mortar prepared with a commercial polymer modifier. Indeed, SSLM can be stable in applications in which it is exposed to or submerged in water for an extended period of time. Similarly, SSLM can be stable in applications in which it is exposed to or submerged in acid for an extended period of time.
[0026] Prior to solidifying, SSLM can have better moldability than sulfur concrete that does not include limestone powder. In one embodiment, the SSLM can have increased flowability, which can make it easier to pour than sulfur mortar that does not include limestone powder. In one embodiment, the SSLM, in its liquid state, has sufficient flowability to occupy formworks when it is poured. Embodiments using fine limestone powder can be more workable than embodiments that do not use fine limestone powder such as sulfur concrete having coarse limestone aggregate or not having any limestone. SSLM can be as durable or more durable than conventional sulfur mortar. Without being bound to any theory, it is believed that the fine limestone powder mitigates crack propagation within sulfur mortar, thereby promoting the durability of the SSLM. Entrained gas cells are not required for such mitigation of crack propagation.
[0027] Sulfur, such as elemental sulfur, can be produced as a by-product when refining hydrocarbons such as crude oil. Some types of crude oil, known as sour crude, can have more than 0.5% sulfur, The sulfur removed from crude oil must be stored or disposed of. In embodiments, the sulfur is disposed of by incorporating it into SSLM.
[0028] In various embodiments, SSLM is used in applications that are not exposed to temperatures greater than 120 degrees C. In one embodiment, SSLM is used as an acid-resistant coating in applications such as flooring, fair coat on walls, structural columns and beams, and process equipment. In one embodiment, SSLM is used in applications in which the SSLM is exposed to water for an extended period of time. SSLM, including SSLM made without plasticizers or other modifiers, can be stable in water in the solid state. In one embodiment, SSLM, in the solid state, absorbs less than 1% water by weight.
[0029] Referring to Table 4, the deterioration in water of an embodiment of SSLM concrete is compared to concrete made with limestone aggregate, dune sand, limestone powder, and sulfur.
[0000]
TABLE 4
Water Stability Comparison
Coarse
Fine
aggregate,
aggregate,
Filler,
type and
type and
type and
content in
content in
content in
Days until
the mix
the mix
the mix
Sulfur
Modifier
deteriorated
#
(%)
(%)
(%)
(%)
(%)
in water
1
Limestone
Dune sand
Limestone
12.5
2.5
Less than
47
28
powder 10
4
2
Limestone
Dune sand
Limestone
15
0
Less than
47
28
powder 10
58
3
Limestone
Dune sand
Fly ash 10
10
2.5
Less than
47
28
133
4
None
Dune sand
Limestone
17.5
0
More than
72.5
powder 10
600
[0030] Although the present invention has been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereupon without departing from the principle and scope of the invention. Accordingly, the scope of the present invention should be determined by the following claims and their appropriate legal equivalents.
[0031] The singular forms “a”, “an” and “the” include plural referents, unless the context clearly dictates otherwise.
[0032] Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.
[0033] Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within the said range.
[0034] Throughout this application, where patents or publications are referenced, the disclosures of these references in their entireties are intended to be incorporated by reference into this application, in order to more fully describe the state of the art to which the invention pertains, except when these reference contradict the statements made herein.
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A sulfur-sand limestone mortar and methods of preparing the sulfur-sand limestone mortar and disposing of elemental sulfur, are disclosed. In embodiments, the sulfur-sand limestone mortar includes elemental sulfur, limestone powder, and sand. Modifiers, such as plasticizers, are not required and are not used in embodiments of the sulfur-sand limestone mortar. In embodiments of the method to prepare the sulfur-sand limestone mortar, each of the elemental sulfur, limestone powder, and sand are heated to at least 140 C, then combined, and then allowed to solidify.
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CROSS-REFERENCE TO RELATED COPENDING PATENT APPLICATION
“A METHOD OF FORMULATING AND PRESENTING SEARCH QUERIES TO A TABULAR DATABASE THROUGH A USER-INTERACTIVE COMPUTER DISPLAY INTERFACE”, John Lawrence (Attorney Docket No. AT9-98-373), filed on the same day as the present application and assigned to the same assignee.
TECHNICAL FIELD
The present invention relates to user-interactive computer supported display technology, and particularly to such user-interactive systems and methods which provide interactive users with user friendly interfaces for database management and access.
BACKGROUND OF THE INVENTION
The 1990's decade has been marked by a technological revolution driven by the convergence of the data processing industry with the consumer electronics industry. This advance has been even further accelerated by the extensive consumer and business involvement in the Internet over the past few years. As a result of these changes it seems as if virtually all aspects of human endeavor in the industrialized world require human/computer interfaces. There is a need to make computer directed activities accessible to people who, up to a few years ago, were computer illiterate or, at best, computer indifferent.
Thus, there is continuing demand for display interfaces to computers and networks which improve the ease of use for the interactive user to access functions and data from the computer. With desktop-like interfaces including windows and icons, as well as three-dimensional virtual reality simulating interfaces, the computer industry has been working hard to fulfill such interface needs. However, in the area of database management, interfaces to the databases appear to be formidable obstacles to a great many users who would have considerable needs for data access. Of course, database access and management historically was one of the original primary computer functions, and, as such, it is full of language and functions developed and communicated between computer professionals. As a result, database management and access may be somewhat esoteric and foreboding to the new computer users in businesses and personal computer situations in which they most benefit from the development of and access to databases. Terms such as relational databases (RDBMS) structured query language (SQL) searches have put off such users. Less sophisticated users find it very difficult to frame SQL search queries out of the relatively complex language. As a result, except for some limited access to databaseS through spreadsheets, the bulk of new computer users have shown a reluctance to venture into database organization and data searching. Accordingly, the computer industries are trying to address the need to make interfaces for database organization and access less foreboding and more user friendly.
SUMMARY OF THE INVENTION
The present invention furnishes one solution to the above needs by providing a data processor controlled interactive display interface through which the user may easily access stored search queries to a database and then initiate selected searches executed by such queries. The interactive interface includes a displayed tree having at least one root node representative of a view into a table from said database and a plurality of subnodes under said root node, each subnode representative of a stored search query for said table view. The interface system also includes means for executing a search represented by a subnode in response to a user selection of said subnode, and means for presenting the results of said executed search on the display. The preferred display layout would have the tree displayed in one region of the display screen and the result of the executed search presented in a screen region next to the tree region. In this manner, the user could select a subnode representative of a particular search query, whereupon the search would be executed and the results presented to the user right next to his tree. Such an arrangement would permit the user to go through a series of searches for, let us say, comparison purposes merely by clicking on a sequence of subnodes with his mouse pointer and immediately viewing his results along side of his tree on the display.
The search interface and method of the present invention is very effective in the searching of databases having tabular organization, such as relational databases. With such databases, the search results presented are preferably tabular and present aspects of the table view represented by the root node. Also, the present invention may be most effectively used when the search queries represented by the various subnodes are in SQL. In this manner, the less sophisticated user is not called upon to structure search queries in SQL. It should also be noted that the displayed tree may have a plurality of root nodes, each of which is representative of a view into a given table in the database.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of a generalized data processing system including a central processing unit in which the database search system of the present invention may be implemented;
FIG. 2 is a diagrammatic view of a display screen on which a tree representative of a portion of a database is shown along side one aspect of a table view resulting from the execution of a subnode represented search query;
FIG. 3 is a diagrammatic view of a display screen like that of FIG. 2 in which a tree representative of a portion of a database is shown along side one aspect of a table view resulting from the execution of a different subnode represented search query;
FIG. 4 is a diagrammatic view of a display screen like that of FIG. 2 except that the aspect of the table view results from the execution of a different subnode represented search query;
FIG. 5 is a diagrammatic view of a display screen like that of FIG. 4 except that the aspect of the table view shown results from the execution of a different subnode represented search query;
FIGS. 6 and 7 are a combined flowchart of the basic elements which are set up in the system and program in a computer controlled display system for creating and using the tree of search queries system of the present invention; and
FIG. 8 is a flowchart of the steps involved in running database search queries according to the set up of FIGS. 6 and 7 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, a typical data processing system is shown which may function as a basic computer controlled system used in implementing the present invention of searching databases through display interface trees of selectable search queries. A central processing unit (CPU) 10 , such as one of the PC microprocessors or workstations, e.g., RISC System/6000(™) (“RISC System/6000” is a trademark of International Business Machines Corporation) series available from International Business Machines Corporation (IBM), is provided and interconnected to various other components by system bus 12 . An operating system 41 runs on CPU 10 , provides control and is used to coordinate the function of the various components of FIG. 1 . Operating system 41 may be one of the commercially available operating systems such as AIX 6000(™) or OS/2(™) (“AIX 6000” and “OS/2” are trademarks of International Business Machines Corporation) available from IBM; Microsoft's Windows 95(™) or Windows NT( 198 ), as well as UNIX and AIX operating systems. Application programs 40 controlled by the system are moved into and out of the main memory random access memory (RAM) 14 and consequently into and out of secondary storage, disk drive 20 as needed. The database search system of this invention, which will subsequently be described in greater detail is implemented as an application program 40 . A read only memory (ROM) 16 is connected to CPU 10 via bus 12 and includes the basic input/output system (BIOS) that controls the basic computer functions. RAM 14 , I/O adapter 18 and communications adapter 34 are also interconnected to system bus 12 . I/O adapter 18 may be a small computer system interface (SCSI) adapter that communicates with the disk storage device 20 . Communications adapter 34 interconnects bus 12 with an outside network enabling the data processing system to communicate with other such systems over a local area network (LAN) or wide area network (WAN), such as the Internet. It should be noted that the database search system of the present invention may be used with respect to databases which are accessed over a network. I/O devices are also connected to system bus 12 via user interface adapter 22 and display adapter 36 . Keyboard 24 and mouse 26 are all interconnected to bus 12 through user interface adapter 22 . It is through such input devices that the user may interactively search databases according to the present invention in the manner to be subsequently described. Display adapter 36 includes a frame buffer 39 , which is a storage device that holds a representation of each pixel on the display screen 38 . Images may be stored in frame buffer 39 for display on monitor 38 through various components such as a digital to analog converter (not shown) and the like. By using the aforementioned I/O devices, a user is capable of inputting information to the system through the keyboard 24 or mouse 26 and receiving output information from the system via display 38 .
There will now be described a simple illustration of the present invention with respect to the display screens of FIGS. 2 through 5. When the screen images are described, it will be understood that these may be rendered by storing an image and text creation programs, such as those in any conventional window operating system in the RAM 14 of the system of FIG. 1 . The operating system is diagrammatically shown in FIG. 1 as operating system 41 . An embodiment of the present invention will be described commencing with the display screen shown in FIG. 2 . This initial display screen is presented to the viewer on display monitor 38 of FIG. 1 . In accordance with conventional techniques, the user may control the screen interactively through a conventional I/O device, such as mouse 26 , FIG. 1, which operates through user interface 22 to call upon programs in RAM 14 cooperating with the operating system 41 to create the images in frame buffer 39 of display adapter 36 to control the display on monitor 38 .
The display interface screen of FIG. 2 shows the interactive interface according to the present invention used to provide the user with a vehicle for searching a relational database or any other type of database covering the problems of a given computer system. Thus, the screen is entitled “Work with Problems”. The interface is organized to permit the user to select an already stored SQL query and to have the search executed. While SQL is the most popular current database query language, other query languages could be used with equal effectiveness. A hierarchical tree having, at a high level, a set of root nodes, such as node 52 , “My Problems”, each represent a table view in the relational database which is presented in a first region 50 of the screen. Each of the root nodes may have a hierarchy of levels of subnodes such as subnode 54 , “PC APPLICATIONS”, each of which represent a stored search query into the table view of the root node. The tree of root nodes and their respective subnodes is, of course, configured for the particular database and desired view tables. The tables used in the illustrations may be conveniently configured by the process described in the copending concurrently filed patent application cross-referenced above.
In the illustration of FIG. 2, the user has selected subnode 54 which represents the SQL query, “SELECT * FROM PROBLEMS WHERE PROBLEM_CODE=‘OPEN ’AND SYSTEM=‘PC APPLICATIONS’”. Upon user selection of subnode 54 , the search represented by the query is executed, and the result is shown by table 53 in screen region 51 which may be considered to be an aspect of table view represented by the root node 52 . Similarly, in the illustration of FIG. 4, the user has selected subnode 55 , “LOTUS NOTES”, which represents the SQL query, “SELECT * FROM PROBLEMS WHERE PROBLEM_CODE=‘OPEN’ AND SYSTEM=‘PC APPLICATIONS’” AND COMPONENT=‘E-MAIL’ AND ITEM=‘LOTUS NOTES 4.X’. Upon user selection of subnode 55 , the search represented by the query is executed, and the result is shown by table 53 in screen region 51 which may be considered to be an aspect of the table view also represented by the root node 52 . It should be noted that in table 53 , the result of the search is identical in FIGS. 2 and 3 even though the search SQL query of FIG. 3 is limited by two additional hierarchical levels.
In the illustration of FIG. 4, the root node 60 , “Problems under the Hardware SLA”, is different from the root nodes in FIGS. 2 and 3 and the selected subnode 56 , “10:15:07”, and represent the SQL query, “SELECT FROM PROBLEMS WHERE THE PROBLEM — IN (SELECT REFERENCE — ID FROM ACTIVE — SLA WHERE BREECH — DATE= 10/06/98 ’ AND BREECH_TIME=‘10:15:07’). This again results in the same table 53 as in FIGS. 2 and 3 which illustrates that different search queries even through different root nodes still may provide the same search results.
FIG. 5 is another illustration of the selection of a subnode 58 under another root node 59 which provides the search results in table 57 , which table is quite different from the table results 53 of FIGS. 2, 3 and 4 .
Now with reference to FIGS. 6 through 8, we will describe a process implemented by the present invention in conjunction with the flowcharts of these figures. The steps in FIGS. 6 and 7 relate to the setting up of the tree structure of this invention which will provide the search queries. First, step 101 , a display tree is created with a plurality of root nodes, each of which have a respective plurality of subnodes at several hierarchical levels. The relational database to be searched is provided, step 102 . A plurality of search queries are created in sets, each relative to a table view of the database, step 103 . A plurality of root nodes in the tree are set to respectfully represent each of a plurality of table views in the database, step 104 . Links are created between each of the root nodes and the particular tables they respectively represent, step 105 . Then there is set up a plurality of subnodes in the tree to respectively represent a plurality of search queries, step 106 . The flow then branches to FIG. 7 via entry point “A”. Step 107 , links are created between each of the subnodes and the stored query represented by the subnode. Then, a process is set up which, in response to the selection of a subnode, will execute the database search represented by the subnode, step 108 . A process is set up for displaying the search results as a table adjacent to displayed tree, step 109 . A process is set up which, responsive to the selection of another subnode, will execute a search in the database using the query represented by the subnode, step 110 , and a process is set up for displaying the results of the subsequent search as a table replacing the table of step 109 .
Now, with reference to FIG. 8, we will describe an illustrative run of a search involving queries set up according to the process described in FIGS. 6 and 7. The search program is run as an application program, either alone or incorporated into a database management system, such as Access(™), dBase IV or dBase 5. First, step 115 , the tree is displayed in one region of a display screen, e.g. region 50 , FIG. 2 . Then, a determination is made, decision step 116 , as to whether the user has selected a subnode representative of a search query. If No, the process is returned to step 116 until there is a Yes decision. Then, the stored search query represented by the subnode is fetched, step 117 , and executed in the database, step 118 . The search results are displayed as a table, step 119 , in a region adjacent to the tree, e.g. region 53 , FIG. 2 . Next, step 120 , a determination is made as to whether the user is finished with the results, step 120 . If Yes, then a further determination is made as to whether the session is over, step 121 . If Yes, then exit, but if No, then the process is branched back to step 116 where a determination is made as to whether another subnode has been selected. If the decision from step 120 is No, the user is still using the results, then the process goes to step 122 where a determination is made as to whether subnode has been selected. If No, then the process remains at step 122 until another subnode is selected, while the last search result table from step 119 continues to be displayed. When another subnode is selected and the decision from step 122 is, thus, Yes then the stored search query represented by the subnode is fetched, step 123 , and executed in the database, step 124 . The search results are displayed as a table, step 125 replacing the last search result table of step 119 in the region adjacent to the tree, e.g. region 53 , FIG. 2, after which the process is branched back to step 120 via entry point “B” where a determination is again made as to whether the user is finished with the search results, and the process then continues as previously described.
One of the preferred implementations of the present invention is as an application made up of programming steps or instructions resident in RAM 14 , FIG. 1, during computer operations. Until required by the computer system, the program instructions may be stored in another readable medium, e.g., in disk drive 20 , or in a removable memory such as an optical disk for use in a CD-ROM computer input or in a floppy disk for use in a floppy disk drive computer input. Further, the program instructions may be stored in the memory of another computer prior to use in the system of the present invention and transmitted over a LAN or a WAN, such as the Internet, when required by the user of the present invention. One skilled in the art should appreciate that the processes controlling the present invention are capable of being distributed in the form of computer readable media of a variety of forms.
Although certain preferred embodiments have been shown and described, it will be understood that many changes and modifications may be made therein without departing from the scope and intent of the appended claims.
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A computer controlled user-interactive display system interface through which the user may access stored search queries to database and then initiate selected searches executed by such queries. The interactive interface includes a displayed tree having at least one root node representative of a view into a table from the database and a plurality of subnodes under the root node, each subnode representative of a stored search query for said table view. The interface system also includes an implementation for executing a search represented by a subnode in response to a user selection of that subnode, and an expedient for presenting the results of said executed search on the display. The preferred display layout would have the tree displayed in one region of the display screen and the result of the executed search presented in a screen region next to the tree region. In this manner, the user could select a subnode representative of a particular search query, whereupon the search would be executed and the results presented to the user right next to his tree.
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BACKGROUND ART
The invention relates to a method of improving a surface of a semiconductor substrate, wherein the surface at least partially includes silicon.
In semiconductor device production, it is more and more important to provide semiconductor substrates of a very high quality. Defects of semiconductor substrates can be of very different origin and may occur in the bulk material of wafers or layers or on the surface of a structure. Deficient wafers, such as wafers or layers with holes or scratches on their surface or with oxide precipitates or so-called “HF-defects”, which are present in or on a wafer and will be apparent by an HF-etch step, are mostly not suitable for further use.
To improve the surface characteristic of a defective wafer, a wafer treatment of a wafer surface such as an etching step or a chemical mechanical polishing (“CMP”) step can be used to remove or to reduce the number or the size of defects at or near the wafer surface. Typical etchants are halogen bearing compounds such as HCl, HBr, HI, HF, and others. The etchant can also be a fluorine bearing compound such as SF 6 , or C x F x . Moreover or in addition, it is possible to treat a defect containing wafer thermally, preferably in a hydrogen bearing environment, to smooth it and to diminish its defects. The thermal treatment can be performed in a furnace or in a tool for rapid thermal processing (“RTP”). According to another approach disclosed in U.S. Pat. No. 6,287,941 B1, a defective wafer such as a cleaved film can be subjected to a combination of etching and deposition at very high temperature using a combination of etchant and deposition gases to result in a better surface quality.
Although such methods lead, in the first instance, to a superficial improvement of the surface condition of a defective wafer by smoothing, abrasion or defect covering of the respective wafer, the known methods are mostly very laborious and the corresponding defects cannot really be repaired. Thus, there remains a need to process defective wafers to increase surface quality.
SUMMARY OF THE INVENTION
The present invention now provides a method of improving a surface of a semiconductor substrate that is at least partially made of silicon, wherein defects present in or on the semiconductor substrate can be really repaired to provide a semiconductor substrate that has a high surface quality. This method comprises a deposition step comprising a selective epitaxial deposition of silicon in at least one hole on the surface of the semiconductor substrate.
The present invention makes it possible to deposit silicon in the hole(s) to seal or to close them selectively with high-quality mono-crystalline silicon material wherein the formation of polycrystalline silicon is avoided, such that the original hole disappears from the surface and the resulting repaired surface provides a high surface quality which is comparable to surfaces which are free from holes or defects from the outset.
In a preferred variation of the invention, the deposition step comprises a selective growth of silicon on at least a part of a side wall of the hole(s). In this manner, holes in the silicon layer lying on another material can be closed by a gradual growth beginning from the side walls of the corresponding hole. This kind of method is, in particular, of interest for closing large holes in SOI structures with high-quality silicon.
In another preferred variation of the invention, the method comprises an etching step applied on the surface of the semiconductor substrate before the deposition step. The etching step comprises an etch-back of at least one defect present on the surface of the semiconductor substrate thereby forming at least one hole on the surface. By this etching step, the at least one defect can be removed leading to at least one hole at the surface of the semiconductor structure which can then be closed with silicon with the result that the original defect can be removed and a nearly perfect repaired surface of the originally defective semiconductor structure can be provided.
According to an advantageous embodiment of the invention, the deposition step is applied at least until the at least one hole is plugged with silicon. In some cases, it can be sensible or sufficient only to plug the hole so that the hole is closed wherein it is of minor interest whether the whole hole is filled with silicon or not. In any case, as a result, the former hole in the surface of the semiconductor structure treated with this method is closed so that this semiconductor structure can be used for further processing.
Preferably, the deposition step is applied at least until the at least one hole is plugged or filled with silicon. In doing so, the former hole can be fully removed and the resulting structure can be provided with a high-quality both at and under the surface.
Advantageously, the etching step comprises a HF-dip to etch-back oxide containing defects at the surface of the semiconductor structure. An HF-etch step removes effectively oxide and thus reveals oxide containing defects at the surface resulting in a formation of holes on the surface which in turn can be closed with the selective deposition of silicon.
According to a preferred embodiment of the invention, in the selective epitaxial deposition, etchant and silicon containing gas are used as source gas. HCl as the etchant and SiH 2 Cl 2 as the silicon containing gas are especially well suited material for providing a high-quality selective deposition of monocrystalline silicon since the respective source gas highly prevents nucleation of silicon on oxide surfaces or walls which would result in a growth of polysilicon. For selective epitaxial growth, favorable etchant concentrations are a few % of the total volume of the source gas.
In another preferred embodiment of the present invention, silicon is deposited in the deposition step up to a thickness corresponding at least to about one half of the diameter of the hole on the surface. This thickness has been shown to be especially advantageous for a solid and durable sealing of the respective hole.
In order to remove contaminants from the etched surface, it has been shown as advantageous to apply a H 2 bake at about 650° C. to 800° C., preferably for about 2 minutes, on the semiconductor structure before the deposition step. This relatively low-temperature H 2 bake leads to an effective removal of contaminants but to a low risk of agglomeration of silicon during the deposition step.
It has been shown to be advantageous to perform the deposition step at about 750° C. This deposition temperature is lower than the temperature used in standard epitaxy processes. That way, agglomeration of silicon can be avoided, in particular if SOI structures with thin silicon top layers are treated with the inventive method.
In a further embodiment of the invention, the deposition step is performed under reduced pressure, for example from about 20 Torr to 80 Torr. The deposition in a reduced atmosphere with this pressure leads to especially good and homogenous silicon formation.
In another variation of the invention, the thickness of silicon on the surface of the semiconductor substrate is reduced before or after the deposition step. This enables a reduction of the final thickness of the treated semiconductor substrate, which can be in particular of importance in repairing of SOI wafers.
BRIEF DESCRIPTION OF THE DRAWINGS
Advantageous embodiments of the invention will be described in the following with respect to the drawing figures in which:
FIG. 1 schematically shows a SOI substrate containing a defect;
FIG. 2 schematically shows the substrate of FIG. 1 after a short HF dip;
FIG. 3 schematically shows the substrate of FIG. 2 after selective deposition of silicon;
FIG. 4 schematically shows after a deeper HF dip;
FIG. 5 schematically shows the substrate of FIG. 4 after selective deposition of silicon;
FIG. 6 schematically shows a hole in a SOI-substrate sealed with silicon in accordance with the present invention; and
FIG. 7 schematically shows another hole in a SOI-substrate sealed with silicon in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 schematically shows a SOI substrate 1 containing at least one defect such as a HF-defect or the shown oxide precipitate 2 . The SOI substrate 1 is only shown exemplarily to demonstrate the principle of the present invention, wherein the present invention can also be used to improve the surface quality of another semiconductor substrate like a silicon wafer or any other substrate having on top at least partially silicon. In particular, it is not necessary to provide a substrate with an oxide layer, as shown in FIG. 1 , to apply the inventive idea of repairing this substrate.
The inventive method is also applicable to other materials such as silicon alloys, for example SiGe structures.
The SOI substrate of FIG. 1 comprises a silicon substrate 3 , on which a buried oxide 4 is formed, and has on top a silicon layer 5 having a certain thickness t 1 and comprising the at least one defect such as the shown oxide precipitate 2 situated at a surface 6 of the silicon layer 5 and extending into the bulk region of this silicon layer 5 . The only one defect shown in FIG. 1 consists in the example shown mainly of silicon dioxide and is only shown exemplarily to illustrate the idea of the invention, wherein in fact considerably more defects as the one defect shown can be present in or on the silicon layer 5 . The oxide precipitate of FIG. 1 shall show exemplarily a “small” defect having a rather small lateral extension being in the order of magnitude of the thickness of the silicon layer 5 or smaller.
According to FIG. 2 , the structure shown in FIG. 1 is subjected to HF leading to an at least partial removal of the oxide precipitate 2 beginning at the surface 6 and continuing in the depth of the oxide precipitate 2 without or with only minimum effects on the silicon layer 5 since HF etches silicon with a much lower rate than silicon dioxide. In the same way, the HF dip treatment can be used to etch-back HF-defects to create space which can be plugged or filled in a subsequent process step described below with defect-free silicon.
The longer the HF dip the deeper is the resulting hole 7 in the surface 6 of the SOI structure 1 . As shown in FIG. 4 , a longer HF dip can result in a hole 17 extending into the buried oxide layer 4 underlying the silicon layer 5 .
FIG. 3 schematically shows the SOI substrate of FIG. 2 after a selective deposition of silicon using Selective Epitaxial Growth (SEG) wherein the dashed lines and the direction of arrow A shall demonstrate schematically the progress of silicon deposition leading to a thickness t 2 of the resulting silicon top layer 8 .
SEG is an epitaxial deposition process which has the advantage that it will prevent, in general, nucleation of silicon on a polycrystalline or an amorphous material like an oxide surface. An epitaxial silicon growth does only occur on mono-crystalline silicon.
Prior to the SEG step, wet cleaning and in situ H 2 bake at about 650° C. to 800° C. for about 2 minutes under a reduced pressure, for example of 20 Torr is applied on the SOI-structure shown in FIG. 2 in order to remove C, O and F contaminants on the surface 6 . If a bulk material such as a silicon wafer shall be repaired instead of the SOI-structure shown in FIG. 2 , the H 2 bake is performed at higher temperatures. If the silicon layer 5 is thinner than 20 nm, temperatures in excess of about 700° C. should not be applied during H 2 bake on the SOI structure 1 to prevent a Si film retraction during SEG. Only in cases in which the film thickness of the silicon layer 5 is higher than 20 nm, the H 2 bake can be performed at temperatures up to 850° C. or higher. Although in comparison with other conventional H 2 bake processes the recommended temperature of the invention for the H 2 bake is relatively low, the contaminants left on the surface 6 prior SEG silicon formation have not such an impact on the electrical properties of the resulting devices since they will be partially consumed or removed during later procedural steps. The H 2 bake is followed by a ramping-up of the temperature up to the temperature of the SEG step.
To avoid an agglomeration of silicon, the SEG of silicon is performed in a reduced atmosphere of about 20 Torr applying a relatively low temperature of about 650° C. to 800° C. and using for instance HCl as an etchant and for instance SiH 2 Cl 2 as the Si gaseous precursor and using H 2 as carrier gas, optionally with some gaseous hydrochloric acid to achieve full selectivity vs. SiO 2 and Si 3 N 4 . For an ultra-thin silicon layer 6 with a thickness t 1 in the range of 3 to 10 nm, the SEG step should be performed at about 750° C. using for example a SiH 2 Cl 2 +HCl chemistry to avoid any severe islands formation during silicon growth. During SEG, the growth rate of silicon should be fairly low which can be achieved by source gas reduction wherein the reaction rate is reduced in the presence of HCl.
As shown schematically in FIG. 3 by the dashed lines, silicon grows during SEG on the surface 6 of the silicon layer 5 , on the open silicon at the side walls of the etched hole 7 as well as on the already grown silicon in such a way that the hole in the silicon layer 6 is gradually closed or plugged with silicon. After a certain process time, a thickness t 2 of silicon with a high surface quality is reached on top of the silicon layer 6 . The non-etched part of the defect 2 and a small unfilled residual part of the etched hole 7 are buried in the structure above the oxide surface where no nucleation occurs.
If the defect shown in FIG. 1 is fully etched away during the etching step and the etching step is performed in such a way that the buried oxide below the silicon layer 5 is not influenced, the defect(s) in or on the silicon layer 5 can be fully removed and replaced by high-quality silicon resulting in a nearly perfect structure having a surface 6 without defects or with only a minimum of defects.
During the SEG deposition step, it can be assumed that the opening of the hole 7 is sealed if the thickness t 2 of the deposited silicon layer is about ½ of the diameter w of the hole 7 . Therefore, a minimum epitaxial thickness t 2 of about ½ of the hole 7 diameter w is necessary in order to seal the opening.
With reference to FIG. 4 , the structure of FIG. 1 is etched deeper than in FIG. 2 during the etching step so that the buried oxide 4 lying under the silicon layer 5 was affected. The resulting hole 17 in the SOI structure 1 has silicon side walls formed by the silicon layer 5 and a bottom of silicon dioxide formed by the attacked buried oxide layer 4 .
As shown schematically in FIG. 5 , the hole 17 of the SOI substrate of FIG. 4 is gradually filled during the SEG process with silicon. At a certain time of growth, the hole 17 is plugged and covered with high-quality mono-crystalline silicon wherein a little cavity 27 can remain in the buried oxide layer 4 which hole 27 is not filled with silicon.
FIGS. 6 and 7 show schematically that the idea of the invention can also be used to improve the surface quality of substrate or structures having on top layer with “larger” holes such as “wells” having a large aspect ratio wherein the width w of the holes is a few times higher than their depth h (w/h>>1). In the examples shown in FIGS. 6 and 7 , the diameter w of the holes 37 and 47 is about 0.5 μm, the silicon top layer 5 has a thickness of about 50 nm and the oxide layer 4 has a thickness of about 150 nm resulting in an aspect ratio of 2.5. The arched lines in the FIGS. 6 and 7 indicate the sequence of epitaxial deposition.
With reference to FIG. 6 , a SOI substrate 10 is shown, the SOI substrate 10 consisting of a silicon substrate 3 , an oxide layer 4 on the silicon substrate 3 and a thin silicon top layer 5 . The SOI substrate 10 has a hole 37 through the silicon top layer 5 and the oxide layer 4 . The hole 37 has in the example shown nearly perpendicular, flat side walls formed, for instance, by photolithography and etching, but can have, in other not shown embodiments of the present invention, also inclined and/or rough side walls. The bottom 39 of the hole 37 is formed by the surface of the silicon substrate 3 and consists, therefore, of mono-crystalline silicon.
In the embodiment shown in FIG. 6 , the surface 6 of the structure 10 can be smoothed and straightened by filling the hole 37 in accordance with the present invention using the Selective Epitaxial Growth of silicon. In the particular case shown in FIG. 6 , a HF dip prior SEG is not necessary but can, for instance if native oxide should be removed from the bottom 39 , be applied. As explained above with reference to FIGS. 3 and 5 , it is furthermore possible to apply a wet cleaning step before SEG.
As also explained above with reference to FIGS. 3 and 5 , prior to SEG a H 2 bake is applied. Then follows a SEG step in accordance with the exemplification of FIGS. 3 and 5 . During the SEG step, silicon grows on the exposed silicon areas of the structure 10 , in particular on the surface 6 of the silicon layer 5 , on the exposed side walls 20 , 21 of the silicon layer 5 and on the bottom 39 of the hole 37 as well as on the already grown silicon. As result, the silicon grows in such a way that the hole 37 is gradually filled during SEG with mono-crystalline silicon wherein it can be possible that at the end of SEG very small buried cavities in the former “large” hole 37 remain which are not overgrown.
FIG. 7 schematically shows an oxide hole or well 47 in a SOI substrate 11 sealed with silicon in accordance with the present invention. The SOI substrate 11 consists, like the SOI substrate 10 of FIG. 6 , of a silicon substrate 3 , an oxide layer 4 and a silicon top layer 5 having a surface 6 with the “large” hole 47 having a more lateral than vertical extension. In contrast to the structure of FIG. 6 , the SOI substrate 11 has on the bottom 49 of the hole 47 a residual thickness of SiO 2 of the not completely etched oxide layer 4 so that the bottom 49 consists of silicon dioxide. Consequently, the silicon growing during SEG does not form on the bottom 49 but only on the surface 6 and the exposed side walls 20 , 21 of the silicon layer 5 as well as on the already grown silicon resulting in an overgrowth of the hole 47 from the sides what can be proceeded till the hole 47 is closed. At the end, there is a smooth, nearly perfect surface of the SOI-substrate formed wherein it is possible that residual little cavities are buried in the treated structure which are not completely filled with mono-crystalline silicon.
In the following, the thickness of the structures as shown in the FIGS. 3 , 5 , 6 or 7 can be adjusted onto certain requirements by a reduction of the thickness of the grown silicon using oxidation, CMP and/or silicon etching. Optionally, the final SOI thickness can also be thinned by an initial reduction of the thickness t 1 of the silicon top layer 5 , for instance by oxidation, CMP and/or silicon etching prior to HF-dip or SEG, or by a combination of initial and final thickness reduction. Furthermore, additional finishing steps, like smoothing annealing can be performed on the final structure.
Thus, the present invention offers a method for repairing defects or closing holes in a surface of a semiconductor substrate consisting at least partially of silicon. The method of the invention can be used to repair defects in silicon substrates as well as in Semiconductor on Insulator Substrates (SeOI) like Silicon on Insulator (SOI) wafers. Regarding the repair of defect(s), the combined action of HF dip and SEG leads not only to a removal of the corresponding defect(s) but also to a plug of the etched hole with high-quality mono-crystalline silicon without a formation of poly-Si in the rebuilt structure.
By means of the inventive method which uses as a new approach the SEG process on a blanket silicon surface, the quality of a defective semiconductor substrate can be enhanced making this substrate attractive for further fabrication processes. SOI substrates repaired with the method of the invention are especially well suited for prospective applications where thicker SOI substrates are required. Depending on the respective top layer specifications, in particular the final thickness (t 1 +t 2 ) of a repaired substrate can be adapted in such a way that the repaired wafer can rejoin the original product group.
SOI wafers repaired with the method of the invention are applicable for the formation of advanced substrates using Direct Substrates Bonding (DSB). Furthermore, the method according the present invention allows repair of defects occurring in structures produced by the so-called SMART-CUT® process.
Moreover, the inventive technology is in particular advantageous for repairing deep defects or for closing large holes in a semiconductor substrate which can not be repaired or closed using the known surface smoothing methods.
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The invention relates to a method of improving a surface of a semiconductor substrate which is at least partially made of silicon. Defects present in or on the semiconductor substrate can be really repaired to provide a semiconductor substrate with a high surface quality. This is achieved by a selective epitaxial deposition in the at least one hole in the surface of the semiconductor substrate. Generally, the deposition step is preceded by an etching step which removes the defects and leaves behind at least one hole that can be plugged or filled with the selective epitaxial deposition of silicon to repair the substrate.
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FIELD OF THE INVENTION
[0001] The present invention relates to the field of liquid coating applicators including, but not limited to painting equipment. More specifically, the invention relates to devices and methods for applying liquids including, but not limited to, paint and similar coatings (such as liquid stain) using an internally-fed manual powered roller or other liquid coating applicator head. The present invention is suitable for applying water or other liquids in the removal of wallpaper.
BACKGROUND OF THE INVENTION
[0002] Prior art paint applicators include conventional rollers, pad applicators and brushes. One advance in the prior art included a single stage internal feed paint roller, exemplified by U.S. Pat. No. 4,732,503 and Des Pat. No. 417,552, the entire contents of each of which are hereby incorporated by reference. Such internal feed paint applicators have found commercial success through wide acceptance and use by consumers. However, such applicators have a deficiency in that they are so long that they cannot be conveniently used in confined spaces such as closets. The paint reservoir and piston extend to such a length as to be impractical for use in confined spaces.
SUMMARY OF THE INVENTION
[0003] The present invention is an improvement over the relatively long length prior art internal feed liquid applicators in that it provides a liquid applicator useable in a shortened configuration or in an elongated configuration, without requiring any extra parts or special assembly or disassembly efforts on the part of the operator. The liquid applicator of the present invention is unlike the prior art applicators in that it includes a telescopically collapsible liquid reservoir. More particularly, the present invention further includes an elongated outer chamber wall having a characteristic length, a liquid delivery piston having a length substantially equal to the characteristic length, with the piston telescopically received in the outer chamber wall, and an elongated intermediate (or inner) chamber wall having a length substantially equal to the characteristic length. In the present invention, the intermediate chamber wall is telescopically received in the outer chamber wall and located circumferentially intermediate the piston and the outer chamber wall. The liquid reservoir and piston may be telescopically expanded either to a fully expanded condition wherein the combined length of the liquid reservoir and piston is about three times the characteristic length, or a partially expanded intermediate condition wherein the combined length of the liquid reservoir and piston is substantially less than half the length of the liquid reservoir and piston in the fully expanded condition.
[0004] The liquid applicator of the present invention may have the liquid reservoir and piston telescopically compressed to about one third the length of the liquid reservoir and piston in the fully expanded condition.
[0005] While a preferred embodiment is disclosed, other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which shows and describes an illustrative embodiment of the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is a perspective view of a prior art manually operated single piston internal feed paint roller applicator, with a roller head shown in phantom.
[0007] FIG. 1A is a perspective view of the prior art applicator of FIG. 1 , except on a reduced scale and showing a piston fully telescoped out of a reservoir in the handle of the applicator.
[0008] FIG. 2 is a perspective view of the dual piston liquid applicator assembly of the present invention with the roller head shown in phantom and with the handle reservoir fully telescopically extended.
[0009] FIG. 3 is a perspective view of the handle reservoir of FIG. 2 fully telescopically collapsed.
[0010] FIG. 4 is a perspective view of the handle reservoir of FIG. 2 in a first partially telescopically extended condition with only one piston extended.
[0011] FIG. 5 is a perspective view of the handle reservoir of FIG. 2 in a second partially telescopically extended condition with both pistons extended.
[0012] FIG. 6 is an exploded view of the handle reservoir of FIG. 2 .
[0013] FIG. 7 is an enlarged view of certain parts of the handle assembly of FIG. 6 showing details of the prior art roller head attachment collar and fill tube subassembly.
[0014] FIG. 8 is an enlarged view of certain parts further exploded from the handle assembly of FIG. 6 showing details of an intermediate chamber wall interior end cap subassembly.
[0015] FIG. 9 is an enlarged view of certain parts further exploded from the handle assembly of FIG. 6 showing details of an end cap subassembly of a piston.
[0016] FIG. 10 is an enlarged view of an end knob and an intermediate wall retaining ring.
[0017] FIG. 11 is an alternative embodiment for a threaded cylinder end ring useful for removable attachment of the inner piston to the intermediate chamber.
[0018] FIG. 12 shows a mating threaded retaining ring threadably receivable on the threaded cylinder end ring of FIG. 11 , along with an alternative rear knob.
DETAILED DESCRIPTION
[0019] Referring to the Figures, and most particularly to FIGS. 1 and 1A , a prior art paint applicator 20 may be seen. This applicator is sold by Wagner Spray Tech Corporation under the PAINT MATE trademark. Applicator 20 is shown in a fully collapsed state in FIG. 1 and (in a reduced scale) in a fully extended state in FIG. 1A . Because applicator 20 has a non collapsible paint reservoir 22 , the fully extended state is generally twice the characteristic length of the applicator reservoir in the fully collapsed state. Applicator 20 also has a paint applicator head such as a roller head assembly 28 . Alternatively, a paint pad assembly (not shown) may be used in place of the roller head assembly 28 .
[0020] In operation, a user fills the reservoir 22 by drawing a piston 24 back to load the reservoir with paint while the inlet valve 26 is in communication with a fill tube (not shown) connected to a source of paint, such as a conventional one gallon paint can or container (not shown). When the reservoir 22 is filled with paint the applicator can be unwieldy when a user desires to paint a surface in a confined space, such as a closet.
[0021] Another prior art device is a short internal feed paint applicator, offered for trim painting applications, such as the applicator sold by the assignee of the present invention under the trademark TRIM-IT. Such short paint applicators are insufficient to reach many surfaces that a user may desire to paint, and as such, users heretofore have needed to purchase both a long handled paint applicator and a short internal feed paint applicator if they desire to paint both hard to reach (distant) surfaces and surfaces in confined spaces.
[0022] The present invention provides an advantage over the prior art by providing a single applicator that is capable of painting (or applying other liquid material) to both distant surfaces and surfaces in confined spaces because of a unique collapsible liquid reservoir that can be used in a relatively short configuration as well as in a relatively long configuration, without disassembly or special adaptation by a user.
[0023] Referring now to FIGS. 2 and 3 , a liquid applicator 30 of the present invention may be seen. Applicator 30 has a collapsible liquid reservoir 32 , which permits applicator 30 to conveniently be used in confined spaces such as closets, by partially collapsing the reservoir 32 , as shown in FIGS. 4 or 5 . In the fully collapsed condition as shown in FIG. 3 , the liquid reservoir 32 of the present invention has the added advantage of requiring less storage space than the prior art applicator 20 . The applicator 30 may use the same paint applicator head such as the roller head assembly 28 or a paint pad assembly (not shown), or another paint applicator head such as a brush assembly (not shown). As a still further alternative, another liquid applicator head may be attached to the applicator 30 , to remove wallpaper, for example.
[0024] As may be seen in FIGS. 2 and 3 , the applicator 30 of the present invention has a first or outer cylinder 34 forming an outer chamber wall 36 , and an intermediate cylinder or chamber 38 formed by an intermediate chamber wall 40 and an inner piston 42 . The intermediate cylinder 38 may also be characterized as forming an intermediate piston 44 with respect to the first cylinder 34 , and thus the overall design may be characterized as a double piston design internal feed paint (or liquid) applicator.
[0025] Referring now also to FIGS. 4 and 5 , the collapsible liquid reservoir 32 for liquid applicator 30 (shown in FIGS. 3 , 4 and 5 without the paint applicator head) is shown in FIGS. 4 and 5 in two alternative “intermediate” conditions between a fully collapsed condition (shown in FIG. 3 ) and a fully extended condition (shown in FIG. 2 ). In FIG. 4 , the intermediate cylinder 38 is telescopically collapsed within the outer cylinder 34 , and the inner piston 42 is telescopically extended therefrom. In FIG. 5 , the intermediate cylinder 38 is telescopically extended from the first or outer cylinder 34 , and the inner piston 42 is telescopically collapsed within the intermediate cylinder 38 . From a user's operational viewpoint, each of the two intermediate conditions are substantially equivalent. It is to be understood that it is not necessary to intentionally or purposefully manually arrange or move the various parts of the applicator 30 from the position shown in FIG. 2 to either of the intermediate conditions of FIGS. 4 and 5 , but that the parts of the applicator 30 of the present invention may assume either of the intermediate conditions during operation by themselves. It is to be further understood that other, “blended” intermediate conditions with the inner piston 42 and the intermediate cylinder 38 partially telescopically extended with respect to each other may occur during operation, without user intervention. In other words, the relative telescoping movement of (and between) the inner piston and the intermediate cylinder may occur in any fashion without affecting the operation of the present invention.
[0026] With the double piston design of the present invention, the user will preferably collapse the collapsible reservoir 32 completely (to the condition shown in FIG. 3 ) prior to filling. To fill the unit, the user then pulls back on a rear knob 46 to load the reservoir 32 with paint or other liquid to the extent desired. One or both of the outer and intermediate cylinders 34 , 38 fill simultaneously or in sequence, which may occur in a random or quasi-random fashion. It is to be understood that it does not matter which fills first or how much liquid each fills with at any given time. The outer and intermediate cylinders 34 and 38 act together seamlessly, and the user does not have to think about or try to control which is filling or when. As with prior art products, if the user pulls the piston out halfway (in air) first, that air will remain in the reservoir and may have to be pushed out (if the roller head is positioned above the reservoir) before applying the liquid contained in the reservoir. It is intended that the user will always begin with the collapsible liquid reservoir 32 in the fully collapsed position (as shown in FIG. 3 ) with the present invention. After being at least partially filled with a liquid (such as paint or stain) the collapsible reservoir 32 of the present invention is preferably gradually telescopically collapsed in steps or stages as the user urges the liquid from the reservoir to the applicator head during operation. One important advantage of the present invention is that, because of the unique double piston, overall size and collapsed length is very short, while the ability to provide extended reach remains relatively long. This allows more convenient use in a tight spaces such as hallways by partially filling the unit, while still being able to reach up to the ceiling using the same tool with a complete fill. Maximum fill capacity is preferably generally equivalent to prior art devices as shown in FIGS. 1 and 1A .
[0027] Referring now most particularly to FIGS. 6-10 , the various parts of the present invention may be seen in more detail. FIG. 6 shows an overall exploded view, and each of FIGS. 7-10 show enlarged fragmentary exploded views of the parts shown in FIG. 6 .
[0028] As shown in FIG. 7 , the present invention may use a retainer 48 that is the same or similar to what is used in the prior art to retain the applicator head. Retainer 48 is preferably received and permanently secured to a cover 50 and an end fitting 52 . End fitting 52 is preferably permanently secured to the outer chamber wall 34 via an integral collar 54 . Retainer 48 also may have a duckbill valve 56 and a retainer disk 58 removably secured thereto by a threaded cap 60 .
[0029] Turning now most particularly to FIG. 8 , the intermediate chamber wall 40 in the form of a right circular cylinder preferably has an intermediate chamber or piston end cap 62 permanently secured thereto. A pair of O-rings 64 seal the piston end cap 62 to an interior cylindrical surface of the outer chamber wall 36 . Piston end cap 62 has an opening 66 in an end wall 68 thereof. Opening 66 provides for fluid communication between the interior of outer cylinder 34 and the interior of intermediate chamber 44 .
[0030] Referring now to FIG. 9 , an intermediate retaining ring 70 is slidingly received over the intermediate chamber wall 40 and is preferably permanently secured to the outer chamber wall 36 (see FIG. 6 ). An inner piston end cap 72 is preferably permanently secured to inner piston 42 , and seals against an inner surface of intermediate chamber wall 40 using a pair of piston O rings 74 . Inner piston end cap 72 preferably has a solid end wall 76 .
[0031] In FIG. 10 , a piston retaining ring 78 is slidingly received over inner piston 42 and is preferably permanently secured to the intermediate chamber wall 40 (see FIG. 6 ). Rear knob 46 is preferably permanently secured to a proximal end of the inner piston 42 . Intermediate retaining ring 70 prevents separation of the intermediate chamber 44 from the outer chamber 34 because of interference between a bore in intermediate retaining ring 70 and the intermediate piston end cap 62 . Piston retaining ring 78 prevents separation of inner piston 42 from the intermediate chamber 38 because of interference between a bore in ring 78 and inner piston end cap 72 . It is to be understood that rings 70 and 78 may be permanently secured to their respective chambers, or they may be forced onto their respective cylindrical walls with a force or interference fit, if desired.
[0032] Referring now most particularly to FIGS. 11 and 12 , in an alternative arrangement, ring 78 ′ may be internally threaded and an externally threaded cylinder end ring 80 may be permanently secured to the intermediate cylindrical wall 40 . Such an arrangement provides removable attachment of the inner piston 42 to the intermediate chamber 38 for cleaning. A similar or identical arrangement may be provided between the outer cylindrical wall 36 and the intermediate cylindrical wall 40 by adding an externally threaded end ring corresponding to ring 80 on the end of the outer cylindrical wall, and providing ring 70 with mating internal threads, to allow selective separation and attachment of the intermediate chamber 38 with respect to the outer chamber 34 . FIG. 12 also shows an alternative rear knob 82 useful for urging the inner piston towards the applicator head to deliver liquid from the telescoping reservoir to the applicator head.
[0033] It is to be understood that to paint (or apply other liquid) with extended reach, the present invention is preferably operated from the fully extended condition to a partially collapsed condition, giving the same or similar reach as is available with the prior art device, while permitting a user to selectively paint (or apply other liquid) in a confined space by partially filling the reservoir and fully telescopically collapsing the reservoir 32 of the present invention.
[0034] It may thus be seen that the intermediate portion of the collapsible reservoir of the present invention may be considered either an intermediate chamber or intermediate piston when the inner piston 42 is not fully collapsed within the intermediate chamber wall 40 . This is because liquids including (but not limited to) paint and similar coating materials are generally incompressible and urging the rear knob 46 towards the roller head assembly 28 will deliver liquid from the outer chamber 34 to the roller because of pressure from the inner piston and liquid (if any) in the intermediate chamber 44 .
[0035] Various modifications and additions can be made to the exemplary embodiments discussed without departing from the scope of the present invention. For example, while the embodiments described above refer to particular features, the scope of this invention also includes embodiments having different combinations of features and embodiments that do not include all of the described features. Accordingly, the scope of the present invention is intended to embrace all such alternatives, modifications, and variations as fall within the scope of the claims, together with all equivalents thereof.
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A liquid applicator having a collapsible liquid reservoir with an elongated outer chamber wall having a characteristic length, and a liquid delivery piston having a length substantially equal to the characteristic length, wherein the piston is telescopically received in the outer chamber wall, and an elongated intermediate chamber wall having a length substantially equal to the characteristic length and wherein the intermediate chamber wall is telescopically received in the outer chamber wall located circumferentially intermediate the piston and the outer chamber wall, wherein the liquid reservoir and piston may be telescopically expanded to either a fully expanded condition wherein the combined length of the liquid reservoir and piston is about three times the characteristic length or a partially expanded intermediate condition wherein the combined length of the liquid reservoir and piston is substantially less than half the length of the liquid reservoir and piston in the fully expanded condition.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to connectors used to interconnect a plurality of wires and a corresponding plurality of circuit elements such as upstanding terminal posts or the conductive paths on a printed circuit board. This invention also relates to connectors for use with a plurality of prearranged conductors or electrical paths to be variously joined or chosen to provide multi-conductive paths. This connector disclosed herein relates especially to connectors for use in interconnecting a multi-conductor flat cable having a specified ground-signal configuration with additional electric circuit elements having a generally different conductive pattern. This connector is also related to devices in which a single or common means causes either a single penetrating means to engage two or more conductors or plural penetrating means to simultaneously engage plural conductors. This invention is also related to devices in which the insulating body of the connector is split or separable at the approximate point of entry of the cable in a plane generally parallel to the axis of the cable, the sections of the insulating body exerting a clamping action on the cable.
2. Description of the Prior Art
The advent of new transmission cables in which a large plurality of wires are encapsulated in a common insulating web has resulted in significant wire handling advantages in the telecommunications and computer industries. These cables are generally manufactured with conductors located on centerlines which are defined by such considerations as the signal propogation speeds required for certain applications. Since these centerline spacings do not generally coincide with the standard centerline spacings for circuit elements used in telecommunications and computer equipment, interconnection problems have been aggravated.
An electrical connector for deploying a plurality of conductors contained in a multi-conductor cable having a flexible dielectric sheath is disclosed and claimed in U.S. application Ser. No. 743,897, filed Nov. 22, 1976 now U.S. Pat. No. 4,076,365. The connector disclosed therein is used in such a manner that the terminaion of a plurality of conductors on one centerline to conductive elements on another centerline can be easily accomplished. U.S. patent application Ser. No. 770,127, filed Feb. 18, 1977, now U.S. Pat. No. 4,094,566, discloses and claims a related connector and assembly method for use in terminating a plurality of ground-signal conductors in a flat cable to a plurality of circuit elements such as contact posts. The posts are arranged in a grid and generally have a ground-signal distribution of the conductors in the flat cable. Each of the connectors shown in these two patent applications represents an improved method for interconnecting flat cables and upstanding posts such as posts mounted on the back-plane of a computer or telecommunications equipment. The standard prior art device used for this interconnection is generally referred to as a paddleboard connector. Paddleboard connectors generally comprise a circuit board with a connector housing mounted adjacent one end. The housing contains a plurality of contact terminals for engaging the posts. A plurality of traces extend from an opposite edge of the circuit board and contact is established with the terminals in the housing. In order to terminate a flat cable to this paddleboard connector the conductors in the flat cable are generally soldered to the conductive traces adjacent this opposite edge of the printed circuit board. This soldering operation involves soldering each individual wire on the cable centerline spacing.
SUMMARY OF THE INVENTION
This invention relates to an electrical connector and a method for interconnecting a first multi-conductor electrical cable, having at least one ground-conductor between adjacent signal conductors, to corresponding circuit elements arranged in a linear array. For example, the connector can be used with a linear array of upstanding contact terminal posts. This invention employs a wire retaining member in which a plurality of conductors can be positioned for insertion into terminals located on the proper centerline spacing for eventual interconnection with the terminal posts. The wire retaining member has a series of grooves extending along an inner face. At one end of the wire retaining member the groove spacing corresponds to the cable conductor spacing. The grooves being located on the post spacing elsewhere on the wire retaining member. Each groove has a width slightly less than the diameter of an individual conductor to retain the conductor in an interference fit. A pair of upstanding ridges or barriers serve to define each groove. Each separate groove and its defining ridges are thus independent of any other groove. The interference fit of the wires in the grooves does not deform or warp the wire retaining member. In the preferred embodiment this wire retaining member serves as a multi-conductor deploying template in which the conductors can be progressively pressed into the grooves.
This connector can also be used to terminate two flat cables. The ground conductor in each flat cable can be commoned by using a laterally extending ground bus having a plurality of upstanding conductor termination members.
The objects of this invention include the provision of an electrical connector for use in interconnecting a large number of conductors to terminal posts mounted in a grid pattern on boards for use in the computer or the telecommunications industries. Square posts having a width of 0.025 in. (0.064 cm.) are commonly used. A spacing between adjacent posts of 0.125 in. (0.318 cm.) is common in the telecommunications industry. Even smaller centerline spacings are common in the computer industry and in other applications. It is, therefore, an object of this invention to terminate the conductors in a flat cable to terminal posts located on standard centerline spacings. Flat cables utilizes for such interconnection generally employ a common dielectric sheath. Quite often this dielectric sheath is composed of polyvinyl chloride. Typically, these cables have a centerline spacing between adjacent conductors which is on the order of 0.03 in. (0.076 cm.). Single cables typically have about 30 conductors. It is, therefore, an object of this invention to provide a connector which will facilitate the interconnection of cables with conductors located on a first centerline spacing, to contact posts located on a second centerline spacing which is typically greater than the first centerline spacing.
In general, the electrical transmission properties specified flat cables of the type used herein, require a ground-signal distribution in the cable which differs from the ground-signal distribution used in standard panel-mounted terminal post grids. For example, it may be necessary to terminate a flat cable having a ground-signal-ground configuration to a two row array of terminal posts having a plurality of adjacent signal posts flanked by ground posts. In general, each of the ground conductors in the cable must be commoned to each of the ground terminal posts. It is, therefore, an object of this invention to provide a connector which can establish the required electrical connections and the required reorientation of ground and signal conductive paths.
In general, it is necessary to mount similar electrical connectors in end-to-end and row-to-row configuration. It is, therefore, an object of this invention to provide a connector having a minimum length and width. For example, a connector utilized to terminate wires to two rows of contact posts located on a 0.125 in. (0.318 cm.) centerline can have a width no larger than 0.250 in. (0.635 cm.). It is, therefore, an object of this invention to provide a connector which utilizes the least possible volume.
One additional object of this invention is to provide a connector which can terminate the conductors in a flat cable on a centerline spacing generally greater than the spacing of adjacent conductors in the cable. By accomplishing this object, the termination of individual conductors is simpler than soldering conductors on the same centerline spacing as is now done with standard paddle-board connectors.
Finally, it is an object of this invention to provide a connector which can be fabricated and assembled with the wires being terminated in a minimum amount of time.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a fragmentary perspective view showing two assembled connectors for use with flat cables with the connectors positioned for mounting on an array of terminal posts.
FIG. 2 is an exploded perspective view showing the relative orientation of the component parts of the connector housing.
FIG. 3 is a section view of the assembled connector.
FIG. 3A is a section similar to FIG. 3 showing the position of a signal conductor.
FIG. 4 is a side view of the connector with the hinged cover member in the open position.
FIG. 5 is a front view showing the pattern of the grooves on the inner surface of the hinged cover member.
FIG. 6 is a side view of the hinged cover member showing the hinged strain relief section.
FIGS. 7 through 10 are schematic views showing the deployment of electrical conductors from the flat cable into the associated grooves in the template on the inner surface of the hinged cover member.
FIG. 11 is a view of the central terminal support housing.
FIG. 12 is a view of the rigid cover member and the template pattern thereon.
FIG. 12A is a side view of the housing member shown in FIG. 12.
FIG. 13 is a view of the auxilliary grounding bus.
FIG. 14 is a side view of the auxilliary grounding bus showing the depending commoning terminal.
FIG. 15 is a schematic view showing a typical wiring pattern used with this connector.
DETAILED DESCRIPTION OF THE INVENTION
The connector disclosed herein can be utilized to terminate two multi-conductor flat cables to the upstanding terminal posts in two rows on a panel member. One specific wiring pattern utilizing this connector is shown in schematic form in FIG. 15. A first cable having conductors arranged in a ground-signal-ground-signal-ground configuration must be terminated to two rows of terminal posts. Each row of terminal posts contains eight signal posts flanked on the end by a ground post. This specific cable contains conductors each spaced apart by approximately 0.03 in. (0.076 cm.). The cross-section of each terminal post is generally square and measures 0.025 in. (0.064 cm.) on each side. Adjacent terminal posts are on a 0.125 in. (0.318 cm.) centerline spacing. The overall dimensions of a connector in accordance with this invention would measure 0.245 in. (0.622 cm.) wide by 1.240 in. (3.150 cm.) in length. Each connector would have a heighth of 1.350 in. (3.429 cm.). This connector would occupy a volume of 0.410 cubic inches (6.178 cm.). A plurality of conductors in a flat cable could be terminated to terminal posts utilizing a connector having this volume. In addition, a connector in accordance with this invention, could be used to terminate the ground conductors of a second flat cable containing a plurality of conductors to the ground conductors in the first cable. By utilizing a similar approach it would also be possible to tap appropriate signal conductors in the second cable to appropriate signal circuits in the first cable and in the terminal post grid pattern.
FIG. 1 shows two side-by-side connectors in accordance with the preferred embodiment of this invention. These connectors are intended for both side-by-side and end-to-end mounting in an array of terminal posts. First multi-conductor cable 2 and auxilliary grounding cable 4 are shown extending into the rear of one assembled connector. Each assembled connector consists of a central main body member 10 flanked on opposite sides by a rigid template cover 12 and a hinged template cover 14, each of which can be molded utilizing a suitable thermoplastic. An auxilliary ground cable cover member 16 is shown mounted on the exterior face of rigid cover member 12. A plurality of contact terminals 18, one of which is shown in the fragmentary view of FIG. 1 are located along the mating face of the connector. A main grounding strip 20 is shown extending along the main body member 10 at a point intermediate the ends thereof. A single ground conductor 8 is shown extending through one wire receiving member on ground strip 20 into the wire receiving portion of the single contact 18 located adjacent one end of the connector. An auxilliary ground bus used with the auxilliary grounding cable 4 is also shown. The auxilliary bus 22 is similar to the main grounding bus 20. Both grounding bus 20, bus 22 and signal terminals 18 are fabricated from a material having spring like properties. Beryllium copper is one such material.
FIG. 2 is an exploded perspective view showing the relative orientation of the four housing components of a connector constructed in accordance with this invention. Appropriate contact terminals and grounding strips are also shown in FIG. 2. The inner template face of hinged cover member 14 is partially revealed in FIG. 2. Note the plurality of grooves extending along the inner face of template 14. The construction of these grooves will be more specifically described in connection with the deployment of the plurality of conductors in a single template member. Contact terminals 18 are located in cavities adjacent to mating face on both laterally facing sides of main housing member 10. It can be seen in FIG. 2 that these contact terminals are in alignment with template grooves and hinged contact member 14 as well as in the rigid cover member 12. Template grooves in cover 12 are not shown in FIG. 2. This template face is shown in FIG. 12.
FIG. 3 is a sectional view of the assembled connector member shown in FIG. 1. The positioning of the individual conductors in each of cables 2 and 4 is apparent from this view. Note that cables extend on opposite sides of main body member 10 as shown. In FIG. 3A taken along a section parallel to FIG. 3 note the nonfunctional position of the contact portion of the main grounding strip 20 which corresponds to the location of a signal conductor. Contact between signal conductors and main grounding strip 20 must be avoided. By merely deflecting the contact portion at the appropriate station on main ground bus 20 as shown in FIG. 3A, contact between the signal conductor and the ground bus is avoided. The functional and nonfunctional positions of the grounding strip shown in FIG. 3 and FIG. 4 can be programmed for a given connector configuration thus enabling the use of standard stamped ground busses. The grounding strip can also be stamped from a suitable blank with the ground bus terminals being omitted at positions which will correspond to the location of signal wires. FIG. 3 also shows position of the auxilliary ground bus 22. Bus 22 is located on the exterior of the rigid cover template 12. A ground commoning contact portion 90 is shown extending through cover member 12 from the exterior surface of the rigid cover to the inner template surface. Note that contact is made in this embodiment with a central ground conductor. This central ground conductor is then terminated to the main ground bus 20 as shown.
FIG. 4 shows the hinged cover member 14 in its open position. Note that electrical contact can be established between appropriate ground or signal terminals in the main housing member and ground and signal conductors in the hinged template cover 14 by merely rotating cover 14 into mating relationship with main body member 10. As these two parts are mated, electrical termination is established by the slotted conductors.
FIG. 5 is a view of the template surface of hinged cover member 14. FIG. 6 is a side view of cover 14. Template cover 14 comprises a cable strain relief member 48 and a generally flat template surface joined by an intermediate integral hinge 46. The template member comprises a generally rectangular member formed of a suitable insulating material. A thermoplastic material would be suitable for use as the hinged template cover member. The template section of hinged cover member 14 has a first laterally extending edge adjacent hinge 46. Immediately adjacent this first edge 54 is a first laterally extending surface 50 which defines the inner face of the hinged template member. A plurality of first grooves 56 extend along edge 54 perpendicular to this first lateral surface 50. A second series of grooves 60 extends from the first edge 54 along lateral surface 50. Each of the grooves 60 extend into surface 50. Each groove of the second series extends from the corresponding groove in the first series of grooves 56. Note that the first series of grooves 56 is generally perpendicular to the second series of grooves 60. This can be most clearly seen in FIGS. 2 and 7 through 10. A second lateral surface 52 parallel to and recessed from surface 50 is defined by a series of indentations between adjacent grooves. A third series of grooves 62 is defined in the region of recessed surface 52. The third series of grooves 62 are formed by pairs of elongated ridges 66. The ridges in each pair extend generally parallel. These elongated ridges generally extend from surface 52 in cantilever fashion with the base being located along recessed lateral surface 52. The end of the second series of grooves 60 and the beginning of the third series of grooves 62 is defined by incremental change in the width of each groove occurring at position 64.
Three laterally extending channels 68, 69 and 72 are located on recessed surface 52. Each of these lateral channels is generally perpendicular to each groove in the third series 62. Lateral channels 68, 69 and 72 receive the wire receiving portion of terminals located on the main ground bus 20 and on contact terminals 18. A series of small ledges 70, each located generally along the centerline of one groove, extends across each of channels 68, 69. Ledges 70 are located at only a portion of the intersections of grooves 62 and laterally extending channel 72. At those positions in which a ledge or stuffer is omitted in channel 72, no conductor will be terminated to an aligned terminal 18. In the configuration shown, ledges 70 in channel 72 are generally aligned with signal conductors. It should be noted, however, that at least one ground conductor will be terminated to a signal post and therefore at least one of the ledges in channel 72 will be used with a ground conductor.
FIGS. 7 through 10 illustrate the deployment of a plurality of conductors in flat cable 2 into appropriate grooves in template cover 14. The insulation has been removed from one end of the cable. As can be seen in FIG. 7, cable 2 is first positioned with the free ends of signal and ground conductors 8 extending generally perpendicular to the first edge of template 14. The free ends of respective conductors extend through each of the first series of grooves 56. Grooves 56 thus serve to locate all of the conductors in cable 2. It can be seen that grooves 60, forming a second series, extend from only a portion of the first series of grooves 56.
In FIG. 8 it should be noted that a portion of the conductors in flat cable 2 are bent adjacent first edge 54 relatively toward the inner surface of template member 14. In FIG. 8 it can be seen that four conductors have been bent. Each of these four conductors is in direct alignment with one of the second series of grooves 60 shown in FIG. 8.
A conductor wiping member represented in FIG. 9 by a cylindrical roller 82 is then positioned against the lateral surface 50 of template member 14. Conductor wiping member 82 is moved along lateral surface 50 away from first edge 54 toward the opposite end of template member 14. The aligned conductors are thus progressively pressed into the appropriate wire receiving grooves in the first, second and third series. The first and second series of grooves have a width which is generally greater than the diameter of the appropriate conductor. The third series of grooves, however, has a width which is generally less than the diameter of one conductor. Therefore, grooves 56 and 60 serve to capture and gain control of individual conductors while the conductor is pressed into an interference fit in grooves 62 which retain the conductor in template member 14.
FIG. 10 shows that each of the four wires have been completely pressed into the appropriate wire deploying template grooves of the hinged template 14. Each conductor now extends across transverse channels 68, 69 and 72. Note that the centerline spacing of the conductors at the intersection of the lateral channels and the longitudinal grooves is different from the centerline spacing between corresponding conductors in cable 2. In fact, the centerline spacing of adjacent signal conductors at channel 72 is equal to the centerline spacing of adjacent signal posts. Each of the four conductors shown is retained in an interference fit in the third series of grooves 62. Since ridges 66 extend from recessed surface 52 in a cantilever fashion, the deformation of each pair of ridges by a single conductor in interference fit in one groove will not be transferred to adjacent ridges and grooves. Deformation of the template surface can not be avoided because of the interference fit of a wire in a groove. Here, each pair of ridges is independently deformed. The absence of cumulative deformation buildup assures that the template will remain dimensionally stable. If the deformation due to conductor-template interference were not isolated, the entire template could become warped as the wires are progressively pressed into appropriate grooves, and alignment between wires, grooves and contact terminals would be lost.
FIG. 11 is a perspective view of the terminal supporting central housing 10. Housing 10 is formed of a suitable insulating material. A synthetic thermoplastic resin suitable for molding and extrusion such as Noryl (a trademark of General Electric Company) can be used. The front view of housing member 10 shown in FIG. 11 is a representation of the side which will eventually mate with the inner surface of rigid cover member 12. As is apparent both here and in FIG. 3, the surface of housing 10, which is to mate with template 14, is generally in the same plane as the outer face of housing 10 in the vicinity of both the ground strip and the contact terminals. Face 26, however, is inclined relative to rear face 28. This inclination allows an appropriate conductor wiping member represented by roller 82 to deploy conductors into the rigid cover member 12 as well as into the hinged template 14. A central cavity 45 located adjacent upper end of housing 10 is adapted to receive a free end of depending contact terminal 90 located on the auxilliary ground bus. Intermediate the upper and lower ends of housing 10 the main ground bus 20 extends along the opposite sides and around the right end of housing 10 as seen in FIG. 11. Ground conductors on either side of central housing 10 can, therefore, be commoned. Ground wires extending across bus 20 would be terminated in the appropriate slotted plate terminal 32. It will be understood that slotted plate contact elements do not extend upwardly from the ground bus at positions corresponding to signal conductors. Contact terminals 13 also have a slotted plate termination portion extending from their upper surface generally perpendicular to the front face of housing 10. A standard post contact portion is located within cavities 36 along front face of housing 10. A longitudinally extending barrier member 44 extends along one side of each terminal 18. Together with similar barrier members in the appropriate template, barriers 44 serve to completely define terminal cavities 36 and the mating face of housing member 10.
FIGS. 12 and 12A illustrate the rigid cover member 12. FIG. 12 shows that the inner template surface of rigid cover member 14 closely resembles the inner face of hinged cover member 14. Note, of course, that the channels extending into this template face are complementary to the channels in hinged member 14. Each conductor, therefore, is deployed into either a channel in hinged member 14 or a channel in the rigid template member 12.
Rigid cover member 12 has a pattern of wire receiving and retaining channels 56', 60' and 62', ridges 66' and transverse terminal receiving recesses 68', 69' and 72' similar to the structures designated by corresponding unprimed numerals on the hinged cover member 14. Cover 14 has a cable strain relief inset 92 located adjacent the rear or cable receiving end. In general, strain relief 92 has a depth equal to one-half the thickness of first cable 2 with suitable cable securing means on the inner surface. A first series of grooves 56' are located along the lower edge of inset 92. The second series of merging grooves 60' extend along the first inner surface 94. Note that first surface 94 is initially parallel to a cable positioned within strain relief inset 92. Surface 94 subsequently is inclined away from the plane occupied for the cable. This inclination is intended to allow receipt of main body member 10 between rigid cover member 10 and hinged cover member 14. As in the hinged cover member the second series of grooves 60' merges with the narrower third series of grooves 62' formed by ridges 66' extending upwardly from recessed surface 96. In the vicinity of terminal receiving recesses 68', 69' and 72' the third series of grooves again extend parallel to the plane occupied by the cable.
As can be best seen in FIG. 2, an auxilliary cover member can be mounted on an exterior face of rigid cover member 12. This auxilliary member is for use when a second cable is to be terminated to appropriate conductors in the first cable. A laterally extending grounding strap is located on the exterior surface of housing member 12. Upstanding slotted plate wire termination portions similar to those on the main ground bus are located along auxilliary ground bus 22. A depending member 88 extends from one side of ground bus 22 with a slotted plate wire termination portion 90 located at its free end. Note that wire termination portion 90 is reversely oriented relative to the wire termination portions 84 and 86 on auxilliary ground bus 22. Wire termination portion 90 extends through a slot in cover member 12 from the exterior surface of the interior surface of cover 12 into contact with the appropriate conductor on the inner surface of the rigid template member. In the particular embodiment shown herein the depending contact member 90 is brought into contact with a ground conductor commoning not only all ground conductors in first cable 2 but all of the ground conductors in cable 4. In this manner two cables are terminated in a connector having a width no greater than twice the centerline spacing of the appropriate terminal posts.
FIG. 15 is a schematic representing the pattern of the conductors in cables when terminated by the preferred embodiment of the connector shown herein. Note that the first cable consists of a plurality of parallel conductors having a signal-ground-signal-ground-signal configuration. The terminal posts are represented by two rows of signal posts in a side-by-side relationship flanked by ground posts. Other similar configurations are sometimes encountered. By properly orienting the template groove means, the terminals 18 and by bending appropriate ground terminals from a functional to a nonfunctional position or shearing the terminals from the ground bus strap, many such wiring patterns can be terminated in the manner disclosed and claimed herein.
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A multi contact electrical connector for interconnection of a ground-signal multi-conductor flat cable to a plurality of electric circuit elements such as terminal posts extending from a panel is disclosed. The connector includes a plurality of discrete terminals in a multi-contact insulating housing with a ground bus mounted on the housing. Conductor template surfaces are located on oppositely facing insulating cover members. The free ends of the conductors in the flat cable are reoriented during assembly of the connector so that proper ground and signal electrical terminations can be established using slotted plate terminal members located on centerlines differing from that employed in the cable itself.
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BACKGROUND OF THE INVENTION
1. Technical Field
The subject invention relates to monoclonal antibodies and uses thereof.
In particular, the invention relates to three monoclonal antibodies, referred to as B1, B3 and B5, which are useful in the treatment and diagnosis of many forms of cancer.
2. Background Information
Current therapies for metastic human cancers, such as radiation or chemotherapy, center on agents that selectively kill rapidly growing cancer cells. Unfortunately, many tumors do not show an unusually fast growth rate compared to important normal tissues, such as bone marrow or the epithelium of the gastrointestinal tract. An alternative group of therapeutic approaches targets unique chemical structures on the surface of tumor cells for therapy, most often employing antibodies that bind selectively to these target molecules. One of these therapeutic approaches employs antibodies that are coupled to cell-killing agents, such as plant or bacterial toxins. These antibody-toxin complexes, immunotoxins, have been shown to be capable of selectively killing tumor cells in model tumor systems in tissue culture and in laboratory animals (Pastan, et al, Cell, 47:641-48 (1986)) . In spite of many attempts to isolate such tumor-specific antibodies for human therapy, there are still very few antibodies identified that selectively bind only to tumor cells and not to other important normal tissues. Isolation of such tumor-specific antibodies is, therefore, of importance for the application of such immuno-directed therapies.
Monoclonal antibody methodology as originally described by Kohler and Milstein (Nature 156:495-97 (1975)) and disclosed in Koprowski, et al. (U.S. Pat. No. 4,172,124) has allowed the isolation of antibodies in pure form for the construction of therapeutic agents. However, two problems have prevented the application of many previously isolated antibodies. First, many monoclonal antibodies reactive with tumor cells also react with important normal human tissues. Secondly, many of the isolated antibodies bind to surface elements that do not efficiently mediate the entry of toxin conjugates into cells by endocytosis. The present invention includes three monoclonal antibodies, B1, B3, and B5, that selectively bind to some human tumors, but not to many important normal tissues. These antibody, when incorporated as the targeting element of an immunotoxin, also has been shown to allow efficient entry of these toxic agents into cells.
Previously, antibodies reactive with the Lewis Y antigen have been isolated and characterized. Recently, two antibodies, BR64 and BR96 have been described (Hellstrom et al., Cancer Res., 50:2183-90 (1990)) that react with Lewis Y antigen, one of which (BR64) is not useful for immunotherapy because of its reactivity to capillaries in human cardiac muscle. BR96, however, shows reactivities that might make an immunotoxin constructed with this antibody potentially useful. The three new monoclonal antibodies, B1, B3, and B5, referred to above, which were isolated using a different cell type for immunizations and using morphologic screening methods, are similar, but not identical, to BR96. These differences in reactivity to tumors, normal tissues, and carbohydrate epitopes make these three new antibodies potentially useful for the therapy and diagnosis of some forms of human cancer.
SUMMARY OF THE INVENTION
The subject invention relates to three monoclonal antibodies, referred to as B1, B3 and B5, and to uses thereof.
B1, B3 and B5 exhibit a strong reactivity toward various mucin-producing, as well as non-mucin-producing primate carcinomas. Thus, these antibodies will be useful in the design of targeted therapeutic agents utilized in the diagnosis and treatment of human cancers.
In particular, the present invention relates to a hybridoma which produces a monoclonal antibody specific for a cell surface epitope wherein said epitope is characterized by expression on normal primate tissue, malignant human cultured cell lines and human tumors.
The present also includes a monoclonal antibody specific the cell surface epitope having the above properties. The class of said monoclonal antibody is IgG or IgM.
The malignant human cultured cell lines, referred to above, are selected from the group consisting of A431, MCF-7, HTB 20, and HTB 33. The normal primate tissue is derived from, for example, the esophagus, bladder or stomach. The human tumor noted above is derived from colon, gastric or ovarian carcinomas.
The present invention also relates to three separate hybridomas having the accession numbers ATCC HB 10569, HB 10572, and HB 10573, respectively.
The monoclonal antibody produced by the hybridoma of accession number ATCC HB 10572 is B1. The monoclonal antibody produced by the hybridoma of accession number ATCC HB 10573 is B3, and the monoclonal antibody produced by the hybridoma of accession number ATCC HB 10569 is B5.
Furthermore, the present invention also includes a method of treating cancer comprising administering to a patient, in need of said treatment, an amount of a conjugate of the monoclonal antibody sufficient to effect said treatment. The monoclonal antibody may be conjugated with, for example, a toxin, radionuclide or chemotherapeutic drug. The toxin may be, for instance, Pseudomonas exotoxin. The chemotherapeutic drug may be, for example, vinblastin or daunomycin.
The present invention also includes a method of diagnosing cancer in a patient comprising the steps of:
drawing a blood sample from said patient;
adding a monoclonal antibody to said sample in an amount sufficient to react with cancer shed antigen to form an antigen-antibody complex; and
detecting whether cancer is present in said patient by measuring the presence or absence of said complex.
Furthermore, the present invention also includes a method of diagnosing cancer in a patient comprising the steps of
removing a tissue or fluid sample from said patient;
adding the monoclonal antibody to the sample; and
visualizing the presence of the antibody in the sample.
The present invention also includes a pharmaceutical composition comprising the monoclonal antibody in a concentration sufficient to inhibit tumor growth, together with a pharmaceutically acceptable carrier.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 represents the antitumor activity of BE-PE Arg 57 in mice. Nude mice (20 g) were injected with 3×10 6 cells subcutaneously on day 0. Treatment with 0.75 ug per dose was given I.P. on days 4, 6 and 8.
DETAILED DESCRIPTION OF THE INVENTION
In order to produce the B1 and B3 monoclonal antibodies of the present invention, mice can be tolerized to normal human kidney membranes and immunized with MCF-7 cells (May et al., American Type Culture Collection Catalog of Cell Lines and Hybridomas, (May et al., ATCC 1988) 6th Ed. (1989), Matthew et al., J. Immunol Methods 100:73-82 (1987) and Willingham et al., Proc. Natl Acad. Sci. USA 84:2474-78 (1987)). In contrast, in order to produce the B5 monoclonal antibodies, mice are not tolerized and can be immunized with A431 cells (May et al., supra). Spleens from the immunized mice are then removed, and the suspended cells can be fused, for example, with AG8 mouse myeloma cells, using polyethylene glycol. Appropriate clones can be selected after screening procedures have been carried out. One screening procedure may involve selecting clones which react with human colon and gastric cancers and not with normal human liver, kidney or colon tissues. This selection process is important for isolating clones that react with tumors, rather than normal tissue, for the use of such antibodies in selective human immunotherapy of cancer.
After subcloning of such antibodies, the isotope of the clones can be determined. The present inventors have established that the isotope for the B1 and B3 clones is IgG 1k , whereas the isotope for the B5 clone is IgM. Antibody can be purified from the supernatant of the clones.
Once the antibodies are produced, their properties may then be characterized. For example, one may characterize precisely which primate tissue epitopes are reactive with the B1, B3 and B5 antibodies.
Reactivity is defined as detectable binding to the surface of living cells using immunohistochemical methods. Such a determination is necessary so that target agents may be designed which are toxic to tumors but not to important normal tissues.
The distribution of reactivity in normal human tissues, human tumors and normal cynomologous monkey tissues is summarized in Table I below.
TABLE I__________________________________________________________________________Immunohistochemical Localization of B1, B3, B5, and BR96 in Normal Humanand Monkey TissuesB1 B3 B5 BR96__________________________________________________________________________NORMAL HUMAN TISSUESLiver (-)(5/5) (-)(5/5) (-)(1/1) (-)(4/4) (+ large bile duct epith) (+ large bile duct)(2/2) (+ large bile duct)(1/1)Kidney (-)(5/5) (-)(5/5) (+/- apic.tub(1/2) (-)(3/4)(+ ap. d.tub)(1/4)Cardiac (-)(6/6) (10/10) (-)(6/6) (-)(6/6)MuscleLung (++ Type II pneum.)(1/2) (+ Type II pneum.)(5/7) (++ Type II pneum.)(1/1) (-)(1/1)Cerebal (-)(2/2) (-)(2/2) (-)(3/3) (-)(2/2)CortexCerebellum (-)(2/2) (-)(2/2) (-)(3/3) (-)(2/2)Spinal (-)(2/2) (-)(2/2) (-)(2/2) (-)(2/2)CordPituitary (-)(1/1) (-)(1/1) (-)(1/1) ndBone (-)(2/2) (-)(1/1) (-)(1/1) (-)(1/1)MarrowAdrenal (-)(1/1) (-)(1/1) (-)(1/1) (-)(3/3)Spleen (-)(1/1) (-)(1/1) nd (-)(1/1)Lymph (-)(1/1) (-)(1/1) (-)(1/1) ndNodeSkin (-)(1/1) (-)(2/2) (-)(2/2) (-)(3/3)Skeletal (-)(1/1) (-)(1/1) (-)(1/1) (-)(2/2)MusclePeripheral (-),?+ cap.endoth.(1/1) (-)(?+ cap. endoth)(1/2) (-)(2/2) (?+ cap.endoth.)(1/1)NerveTonsil (+++ epith.)(2/2) (++++ epith)(2/2) (+++ epith.)(2/2) ndEsophagus (+++ diff. epith.)(2/2) (+++ diff. epith.)(2/2) (+++ diff. epith)(1/1) (+++ diff epith)(4/4)Small (+ mucin)(4/4) (+ mucin)(3/3) (+++ ap muc. gran.)(3/3) (+++ muc.)(3/3)BowelStomach (++++ glnds, muc.)(3/3) (++++ glnds, muc.)(3/3) (+++ glnds, occ het)(3/3) (++++ glnds, muc.)(4/4)Normal (-)(7/7) (weak het. epith)(6/6) (++ het. muc.)(2/2) (-;3/4)(het. +;1/4)ColonBladder (+++ epith.)(3/3) (+++ epith)(3/3) (+++ epith.)(3/3) (+++ epith.)(3/3)Pancreas (#1 = het. + ac.; ducts; (+++ het, d & ac.)(2/2) (+++ d & ac.)(1/1) (+++ het ac. & muc.)(2/2) (#2 = + acini & ducts)Salivary (+ acini & ducts)(1/1) (+++ d & ac.)(1/1) (++++ ac. & d.)(1/1) (+++ ac. & d.)(2/2)GlandMammary (-)(1/1) (het. + ducts)(1/1) (+++ d, het glnds)((2/2) (het. + ducts)(1/1)GlandEpididymis (-)(1/1) (-)(1/1) (-)(1/1) ndThyroid (-)(1/1) (+++ colloid, - epith)(1/1) (-)(1/1) (-)(1/1)Para- (-)(1/1) (-)(1/1) (-)(1/1) ndthyroidOvary (-)(2/2) (-)(1/1) (-)(2/2) ndFallopian (-)(1/1) (-)(1/1) (+/het)(1/1) ndTubeTrachea nd (++++ epith.)(1/1) nd ndPlacenta nd (++++ fetal endoth.)(1/1) nd ndNORMAL CYNOMOLOGOUS MONKEY TISSUESLiver (-)(1/1) (-)(1/1) (-)(1/1) (-)(1/1)Kidney (-)(occ. glom.)(1/1) (+ ap dt, gl. caps.)(1/1) (+ ap tub, gl. caps.)(1/1) (-)(1/1)Brain (-)(2/ 2) (-)(2/2) (-)(1/1) (-)(2/2)Cerebellum nd nd (-)(1/1) ndSpinal (-)(1/1) (-)(1/1) (-)(2/2) (-)(1/1)CordPeriph. nd nd (-)(1/1) ndNerveSpleen nd nd (-)(1/1) ndLymph nd nd (-)(1/1) ndNodeSkin (-)(1/1) (-)(1/1) (-, ex. + seb. glnds)(1/1) ndSkeletal nd nd (-)(1/1) ndMuscleEsophagus (+++ diff epith)(1/1) (++ diff epith)(1/1) (+++ diff epith)(1/1) (+++ diff epith)(1/1)Small (-)(1/2)(+ muc gran)(1/2) (-)(2/2) (++ ap muc. B glnds)(1/1) (-)(2/2)BowelStomach (het + glnds)(1/2) (+++ glnds)(2/2) (+++ glnds)(1/1) (+++ glnds, het.)(1/1)Colon (-)(1/1) (-)(1/1) nd (-)(1/1)Bladder (-)(1/1) (+/-)(1/1) (+++ epith)(1/1) ndPancreas (-; + muc)(2/2) (-; + muc)(3/3) (++ het ac.)(2/2) (+/- het)(2/2)Salivary (het +++ a & d)(2/2) (++ het a; ++ d)(2/2) (++ het a; ++ d)(3/3) (++ het a; ++ d)(2/2)GlandMammary (het +)(1/1) (het. + g; ++ d)(1/1) (het ++ g & d)(1/1) ndGlandsThyroid (-)(1/1) (-)(1/1) (-)(3/3) (-)(1/1)Para- nd nd (-)(1/2)(het +)(1/2) ndthyroidOvary nd nd (-)(1/1) ndVaginal nd nd (++ ++)(1/1) ndGlandsUterine (-)(1/1) (-)(1/1) (++ apic. muc.)(1/1) ndCervixUterine (-)(1/1) (+ deep glands)(1/1) (++ deep glands)(1/1) ndEndo-metriumThymus (-)(1/1) (-)(1/1) (-)(1/1) ndTrachea (-)(1/1) (+ apic epith, het gl.)(1/1) (+ apic epith & gl)(1/1) ndTongue (-)(1/1) (+ diff. epith)(1/1) (++ diff epith)(1/1) nd__________________________________________________________________________ Immunohistochemical analysis was performed on cryostat sections of freshfrozen tissues, postfixed in acetone and incubated with primary antibodies at 10 μg/ml except where indicated. Labeling was then performed using affinitypurified goat antimouse IgG conjugated to horseradish peroxidase, developed using diaminobenzidine, then treated with hematoxylin followed by osmium tetroxide. (- = no localization; + = moderate; ++ strong)(x/y = x examples of this pattern seen in y samples tested)(het = heterogeneous) nd = not determined.
As shown in Table I, the B1, B3 and B5-reactive epitopes are all found in varying amounts in the mucins of the stomach and small bowel, in the differentiated cell layer in the esophagus, in the epithelia of the tonsil, trachea and urinary bladder. These epitopes or antigens, which react with the B1, B3 and B5 monoclonal antibodies, can also be found in various other epithelia in a heterogeneous distribution, such as in the pancreas, salivary gland and mammary gland. B3 has the ability to react with the fetal endothelium, suggesting that the B3 monoclonal antibody represents an antigen expressed in fetal development.
Furthermore, as shown in Table I, the overall pattern of reactivity of the B1, B3 and B5 antibodies is different from the pattern of reactivity of a previously isolated antibody termed BR96 (Hellstrom et al., Cancer Res. 50:2183-90 (1990)). BR96 demonstrates some of the same reactivity patterns as observed with B1, B3 and B5. For example, BR96 reactivity is particularly notable in distal tubules in human kidney, as is B1 and B3 reactivity. However, there are distinct differences between these four antibodies in certain sites, such as in kidneys tubules, type II pneumocytes in the lung, mucin in the colon and in pancreatic ducts. For example, BR96 reactivity is not present in mucin in normal human colon sample, as is B5 reactivity. Such information can be significant in determining whether a monoclonal antibody administered for therapeutic purposes will be toxic with respect to normal tissues.
The above four antibodies can also be evaluated in normal monkey tissues (See Table I). Tissues similar to those in the human samples are reactive; however, similar to the human tissues, there are distinct differences between B1, B3, B5 and BR96 reactivity in kidney tubules, small bowel mucin, bladder epithelium, pancreas, cervical mucin, endometrial glands, and the epithelium of trachea and tongue. These differences indicate that each of these antibodies recognize different epitopes. Thus, the chemical structures of the epitopes are different.
Various cancer cell lines can also be examined for reactivity with B1, B3, B5 and BR96 using immunofluorescence. The results of such a study are shown in Table II presented below.
TABLE II______________________________________Immunofluorescence Localization of B1, B3, B5, and BR96On Human Cultured Cell LinesCELLLINE B1 B3 B5 BR96______________________________________A431 (epi- +++ het ++++ het ++++ het ++++dermoidCa)MCF-7 ++++ ++++ ++++ ++++(breast Ca)OVCAR-3 - - ++++ het ++++(ovarianCa)KB - +/- het ++++ het -(cervicalCa)HT-29 + ++++ ++++ het +/-(colon Ca)MDA-MB- ++++ ++++ nd ++++468(breast Ca)DU145 + het ++ het ++++ het ++++(prostateCa)HTB20 +++ +++ ++++ het ++ +(breast Ca)HTB33 +++ +++ het ++++ het +++(cervialCa)______________________________________ Het = heterogeneous; (-) = negative; (+ = weakly positive; ++ = moderate; +++ = strong; ++++ = very strong). nd = not determined.
As clearly shown in Table II, B1, B3, B5 and BR96 react with some cell lines uniformly, However, there are differences in reactivity, especially for OVCAR-3, KB and HT-29 cells. Again such data suggests that the epitopes recognized by four antibodies are different from a structural standpoint. Furthermore, such differences in epitope structure and therefore in reactivity with monoclonals may be an advantage in therapy in some patients.
Tumors can also be examined for the expression of antigens which react with the 4 antibodies, using peroxidase immunohistochemistry. Table III (below) shows that the B1, B3, B5 and BR96 antibodies react well with carcinomas of colon and gastric origin, and mucinous ovarian carcinomas. Reactivity can be detected in a smaller number of breast, esophageal and other carcinomas.
TABLE III__________________________________________________________________________IMMUNOHISTOCHEMICAL REACTIVITIES OF HUMAN TUMORSWITH B1, B3, B5, and BR96B1 B3 B5 BR96__________________________________________________________________________Colon Ca (++ het cells & mucin)(3/3) (++++ cells & mucin)(9/12) (+++ het)(3/3) (+++)(3/3) (het ++)(3/12)Gastric Ca (++++ cells & mucin)(3/4) (++++)(3/4) (+++)(1/1) (++++)(3/4)Overian Ca (mucinous = +++ cells & mucin) (mucinous = ++++)(2/2) (mucinous = +++)(1/1) (+++ mucinous)(1/1) (1/1);(cystadenoCa = het +)(2/3) (cystadenoCa:(+++)(4/20) (cystadenoCa:het +++) (+ het cystadenoCa) (het ++)(6/20) (2/2) (1/2)Breast Ca (het +)(1/2) (+++ het)(14/21) (-)(2/2) (+++)(5/7)Esophageal nd (het +)(4/9);(++++)(3/9) nd ndCaProstate Ca nd nd (+++)(1/1) (++ het)(2/2)Cervical nd (het +)(1/1) (-)(1/1) ndCaEndome- nd (het ++)(1/1) (++)(1/1) ndtrial CaLung Ca nd (het +)(1/3) nd nd__________________________________________________________________________ Immunohistochemical analysis was performed on cryostat sections of freshfrozen tissues, postfixed in acetone and incubated with primary antibodies at 10 μg/ml except where indicated. Labeling was then performed using affinitypurified goat antimouse IgG conjugated to horseradish peroxidase, developed using diaminobenzidine, then treated with hematoxylin followed by osmium tetroxide. (- = no localization; + = moderate; ++ strong)(x/y = x examples of this pattern seen in y samples tested) (het = heterogeneous) nd = not determined.
The results of Tables I, II and III indicate that B1, B3 and B5 react with many common tumors and appear to react with a limited number of normal tissue sites. In addition, these antibodies show distinct differences in reactivity in some varying tissue samples indicating that the precise epitopes they detect are different.
When MCF-7 cells bearing the B1, B3 and B5 epitopes are metabolically labelled using radioactive amino acids, then extracted and the extracts immunoprecipitated, the reactive species of molecules that are precipitated by B1, B3 and B5 can be analyzed by gel electrophoresis and auto radiography. B1 aand B3 specifically immunoprecipitate protein bands of a very high molecular weight (>250,000 Daltons), consistent with their reactivity with high molecular weight mucins. Because B5 is an IgM antibody, for technical reasons this method is unable to show specifically reactive proteins.
Monoclonal antibodies B1, B3 and B5 can serve as targeting agents for the construction of immunotoxins, in which the monoclonal antibody is linked to a toxin, for example, Pseudomonas exotoxin (see Table IV below). As previously disclosed in Pastan, et al. (U.S. Pat. No. 4,545,985) conjugates of Pseudomonas exotoxin and monoclonal antibodies show efficacy in killing cells that are targeted by the epitope-reactive site of the antibodies. Constructions made by linking B1, B3 or B5 to such toxin would then be introduced into patients that had tumors that were reactive with these monoclonal antibodies, and the immunotoxins would bind to and kill the tumor cells within the patient. Normal tissues that were also reactive with these monoclonal antibodies would be affected if the antigenic sites were accessible to the blood circulation. In the case of many of the sites of expression of antigens reactive with B1, B3, and B5, the reactive epitope appears by immunohistochemistry to relatively inaccessible to the circulation, such as the reaction with mucins in the lumen of the gastrointestinal tract. Thus, it is not possible to predict with total certainty what the toxic effects of such immunotoxins would be in a human patient. Tumor cells that express these surface antigens, however, are rarely in a location that would render them inaccessible to the immunotoxin, and the tumor cells should therefore, be susceptible to targeted cell killing by immunotoxins constructed with B1, B3 or B5.
TABLE IV______________________________________Activity of Immunotoxin Composed of B3 and aPseudomonas Exotoxin Mutant in Which Lysine 57is Converted to Arginine (B3-PE.sup.Arg57) ID.sub.50 B3-PE.sup.Arg57 MOPC-PE.sup.Arg57Cell Line ng/ml ng/ml______________________________________A431 Epidermoid Ca 0.2 >100MCF-7 Breast Ca 0.3 >100______________________________________ ID.sub.50 is the concentration of agent that inhibits protein synthesis b 50% in a 16 hour incubation.
In addition to bacterial or plant toxins conjugated to monoclonal antibodies, other effector agents may be used together with targeted monoclonal antibodies to treat or diagnose human cancer. For example, radionuclides conjugated to antibodies that bind to tumors can produce cell killing based on the high local concentration of radiation. Chemotherapeutic drugs, for example, vinblastine or daunomycin, can be coupled to antibodies and delivered at high concentration to cells that react with the antibodies. B1, B3, and B5 may provide a targeting mechanism for such combination of effector agents that could produce successful regression of reactive human tumors when introduced into patients.
In addition to the targeting of immunotoxins to tumors in a cancer patient, these antibodies also recognize materials such as surface mucins on tumor cells that would be expected to be shed into the surrounding tissues, picked up by the blood stream, and detectable in blood samples taken from distant sites. Such shed antigens have proven to be useful in the diagnosis of primary and recurrent cancers using antibodies that react to these shed antigens. A currently useful example of this is the CA125 antigen that can be assayed in sera from patients with ovarian cancer to predict recurrence or to confirm primary diagnosis of tumor. It is possible, therefore, that B1, B3 and B5 may be useful in the diagnosis of tumors.
Also, the selective reactivity of these antibodies with certain types of tumor cells could be exploited for anatomic pathological diagnosis of tumors, clarifying the type and origin of tumors, and whether a particular group of cells represents a recurrence of a previous tumor or the development of another primary tumor elsewhere. Such a diagnostic determination can be useful for the subsequent planning of anti-tumor therapy in each particular patient. In particular, immunohistochemical pathologic diagnosis in tissue sections (e.g., biopsies) or cytological preparations (e.g., Pap smears, effusions) can be performed using the monoclonal antibodies of the present invention.
Another potential use of such targeting antibodies could be in the diagnosis of macroscopic foci of tumor using antibodies B1, B3 or B5 coupled to radioisotopes that could be detected either by external body scanning (imaging diagnosis) or by localization using radiation detector probes at the time of exploratory surgery.
In addition to the initial clones of B1, B3 and B5 isolated as mouse monoclonal antibodies, variations of the constant regions of these antibodies incorporating constant regions of other species, such as human, could be performed, in which the resulting antibody would display less immunogenicity as a foreign antigen itself when introduced into a human patient. Pharmaceutical compositions can also be made using the monoclonal antibodies.
Also, the genes responsible for the variable regions of these antibodies could be isolated and targeting agents constructed using these variable region genes in tandem with genes for other proteins, such as toxin genes, or other effector proteins that could direct cell killing either directly or through the activation of endogenous mechanisms, such as the immune system. The variable regions of immunoglobulin genes encode the antigen binding site which enables the chimeric antibody toxin protein to bind to and kill target cells expressing the antigen reacting with antibodies B1, B3, and B5.
The present invention can be illustrated by the use of the following non-limiting examples.
EXAMPLE I
Production of the B1, B3 and B5 Monoclonal Antibodies
The human tumor cell lines OVCAR-3, KB, MCF-7, HT-29, MDA-MD-468, DU145, HTB20, and HTB33 have been previously described (Hay et al., American Type Culture Collection Catalog of Cell Lines and Hybridomes, 6th Ed. (1988)). For antibodies B1 and B3, mice were tolerized to normal human kidney membranes (Matthew et al., J. Immunol. Methods 100:73-82 (1978) and immunized with MCF-7 cells using methods previously described (Willingham et al., Proc. Natl. Acad. Sci. USA 84:2474-78 (1987)). For antibody B5, mice were not tolerized and were immunized with A431 cells. Spleens from immunized mice were removed and the suspended cells were fused with AG8 mouse myeloma cells. The resulting clones were screened two weeks later employing the ScreenFast (Life Technologies, Inc. Gaithersburg, Md.) large scale screening chamber using rhodamine indirect immunofluorescence on living MCF-7 and A431 cells for B1 or B3, and B5, respectively. Selected clones were secondarily screened using peroxidase immunohistochemistry on cryostat sections of human tumors and normal tissues. Clones B1, B3 and B5 were selected that reacted with human colon and gastric cancers, and not with normal human liver, kidney or colon. After sub-cloning, the isotypes of these clones was determined to be IgG 1k for clones B1 and B3, and IgM for clone B5. Antibody was purified from the supernatants of these clones using serum-free defined culture media and ammonium sulfate precipitation.
EXAMPLE II
Determination of Distribution of Antigens Reactive with Antibodies B1, B3 and B5 In Human Tumor-Free Tissues, Human Tumors And Monkey Tissues
Samples of normal human tissues, Cynomologous monkey tissues, and human tumors were fresh-frozen and cryostat sections were prepared for peroxidase immunohistochemistry as previously described (Willingham, FOCUS 12:62-67 1990)) using B1, B3 and B5 as primary antibodies. Localization of antibodies was detected by development of the peroxidase substrate reaction using diaminobenzidines. Tissues sections demonstrated major reactivies of B1, B3 and B5 in the epithelium of the tonsil, stomach, esophagus, and bladder, as well as in mucins of the small bowel and colon. Similar localization was found in monkey tissues in esophagus, small bowel, stomach, bladder, salivary gland, and pancreas with some differences being noted between the different antibodies (see Table I). Human tumors showed strong reactivity for B1, B3 and B5 in carcinomas of colon, stomach, ovary, and esophagus, with variable localization seen in carcinomas from breast, cervix, prostate, endometrium and lung (see Table III). All localizations, except as noted in Table I, represented antigen reaction that appeared to be on the surface of the cells, making these sites potential targets for immunotherapy.
EXAMPLE III
Determination of the Effectiveness of BE-PE As An Anti-Tumor Agent
B3 was coupled to Pseudomonas exotoxin as previously described (Willingham et al., Proc. Natl. Acad. Sci. USA 84:2474-78 (1987)). To do this, a mutant form of PE in which lysine 57 of PE was mutated to arginine (PE Arg 57) was used. The immunotoxin was purified and tested in tissue culture where it was shown to kill target A431 and MCF-7 cells (Table V). A control antibody (MOPC 21) was also coupled to PE Arg 57 and it had no cell killing activity. B3-PE Arg 57 was then given intraperitoneally to mice. The mice had been implanted with 3 million A431 cancer cells on day 0, and by day 4 had small cancers which were rapidly growing. The immunotoxin was given IP on days 4, 6, and 8 and, as shown in FIG. 1, the tumors regressed and apparently disappeared, whereas, in the control animals treated with diluent, the tumors grew rapidly.
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The subject invention relates to monoclonal antibodies and uses thereof. In particular, the invention relates to three monoclonal antibodies, referred to as B1, B3, and B5, which are useful in the treatment and diagnosis of many forms of cancer.
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FIELD OF THE INVENTION
This invention relates to a method for preparing organosilanes containing silicon-bonded oxime groups and, more particularly, to that method comprising reacting a halogenosilane with an alkali metal oxime.
DESCRIPTION OF THE PRIOR ART
Hithertofore, organosilanes containing silicon-bonded oxime groups, i.e., ketoximosilanes, have been prepared by dehydrohalogenation between an oxime, such as, 2-butanone oxime or acetophenone oxime, and a haloganosilane, such as, tetrachlorosilane or methyltrichlorosilane, in the presence of an amine, such as, pyridine or α-picoline, as an acid acceptor in an organic solvent, such as toluene or diethylether, followed by distillation of the liquid product (see U.S. Pat. No. 3,189,576). This method of the preparation of organosilanes is disadvantaged for the following reasons. (1) The reaction system concerned has the potentiality of explosive hazards caused by an extraordinary exothermic reaction when an acidic condition is inadvertently generated in the reaction system by the presence of some acid impurities, e.g., organic, inorganic and Lewis acids (see Chemical & Engineering News, page 3, Sept. 2, 1974). (2) A similar potentiality of explosive hazards exists inherently in the reaction system by the presence of the by product, formed by the reaction of the acid acceptor and hydrogen chloride in the dehydrochlorination, which is also a sort of acidic impurities. (3) Salts formed by interaction of the amine compound and hydrogen chloride tend to become existent in the resulting organosiloxane product, such salts present in the products being hardly removed.
OBJECT OF THE INVENTION
It is therefore an object of this invention to provide a method for preparing organosiloxanes containing silicon-bonded oxime groups which are free of one or more of the above-mentioned disadvantages encountered in the conventional methods.
SUMMARY OF THE INVENTION
This invention provides a method for preparing organosilanes represented by the general formula
R.sub.a.sup.1 Si(ON═Y).sub.4.sub.-a
where R 1 is a substituted or unsubstituted monovalent hydrocarbon group, Y is a group denoted by R 2 R 3 C═ or R 4 C═, R 2 and R 3 being each substituted or unsubstituted monovalent hydrocarbon groups, which may be indentical or different, and R 4 being a substituted or unsubstituted divalent hydrocarbon group, and a is 0, 1, 2 or 3, which comprises reacting (a) a halogenosilane represented by the general formula
R.sub.a.sup.1 SiX.sub.4.sub.-a
where R 1 and a are as defined above and X is a halogen atom with (b) an oxime represented by the general formula
Y═NOM
where Y is as defined above and M is an alkali metal.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the method of this invention, the alkali metal halide formed by the reaction of the above-mentioned halogenosilane and metal oxime is safe from inducing any extraordinary oxothermic reactions, since it is chemically neutral. Further advantageously, the method of the invention can be carried out, using no conventional acid acceptors, such as, pyridine and α-picoline, which make obstacles to post-reaction treatments. Furthermore, according to the method of the invention, it is unnecessary to remove amine chloride from the reaction product.
The halogenosilanes are one reactant useful in the method of the invention are represented by the general formula
R.sub.a.sup.1 SiX.sub.4.sub.-a
where R 1 is a substituted or unsubstituted monovalent hydrocarbon group, X is a halogen atom, and a is 0, 1, 2 or 3. Illustrative of the groups denoted by R 1 are alkyl groups, such as, methyl, ethyl, isopropyl, 2-ethylhexyl and dodecyl groups; alkenyl groups, such as, vinyl, allyl and decenyl groups; aryl groups, such as, phenyl, naphthyl and xenyl groups; aralkyl groups, such as, benzyl group; and halogen- or cyano-substituted derivatives thereof. Besides, illustrative of the halogen atoms denoted by X are chlorine, bromine and iodine.
The metal oximes as the other reactant useful in the method of the invention are respresented by the general formula Y═NOM where Y is a group denoted by R 2 R 3 C═ or R 4 ═C═, R 2 and R 3 being each a substituted or unsubstituted monovalent hydrocarbon group exemplified by the same groups as R 1 above, which may be indentical or different, and R 4 being a substituted or unsubstituted divalent hydrocarbon group, and M is an alkali metal. Illustrative of the groups denoted by R 4 are the groups expressed by the following formulas.
______________________________________(1) (CH.sub.2).sub.5(2) (CH.sub.2).sub.6(3) ##STR1##(4) CF.sub.2(CF.sub.2).sub.3CF.sub.2(5) ##STR2##(6) ##STR3##______________________________________
besides, illustrative of the alkali metals denoted by M are lithium, sodium and potassium. Thus, the examples of the metal oxime are lithium, sodium or potassium oximes derived from acetone oxime, acetophenone oxime, benzophenone oxime, 2-butanone oxime, 2-pentanone oxime, cyclohexanone oxime, 2, 4-dimethyl-3-pentanone oxime and 2-nonanone oxime.
In order to obtain ketoximosilanes by the method of the present invention, the above-described halogenosilane is added to the metal oxime which has, preliminarily, been formed in a reactor through reaction between the oxime and alkali metal used in a molar ratio of from 1:1 to 1:2, preferably equimolar, and then the mixture is subjected to reaction. It is preferred that the reaction is carried out in a solvent, such as, benzene, toluene, xylene, dibutylether or dioxane. The reaction temperature is generally between -70° C. and 200° C., preferably, -10° C. and 150° C. It is however most convenient that the temperature is in the range from room temperature to the reflux temperature of the solvent used. The amount of halogenosilane added in this case is at the most an equimolar amount relative to the metal oxime. The organosilane thus obtained is isolated from the reaction mixture by any known purification process.
The ketoximosilanes obtained in accordance with the method of the invention are useful as intermediates for the production of various kinds of siloxanes, particularly room temperature curing silicone rubber compositions.
The following examples are given to illustrate the invention.
EXAMPLE 1
Into a 4-necked 1-liter flask were put 500 ml of toluene and 23 g (1 mole) of metallic sodium, followed by vigorous agitation at the reflux temperature of toluene, to finely divide the metallic sodium. To the resulting mixture was slowly added dropwise 87.1 g (1 mole) of 2-butanone oxime to be converted to a paste-like consistency which was then cooled down to room temperature. Thereupon, 45 g (0.3 mole) of methyltrichlorosilane was added dropwise to the content of the flask with removal of the heat of reaction by keeping the flask in a cold water bath followed by reaction at the reflux temperature of the solvent for 3 hours.
After completion of the reaction, the reaction mixture was filtered, and the filtrate was stripped of toluene, to obtain 89.5 g of liquid product. The yield of the product based on the methyltrichlorosilane was 99%.
The product was identified with a silane containing silicon-bonded oxime groups by infrared absorption spectroscopy, nuclear magnetic resonance and elementary analysis, expressed by the following molecular formula. ##STR4##
EXAMPLE 2
Procedures similar to that of Example 1 were repeated with the alteration that the various halogenosilanes in varied amounts as indicated in Table I were employed instead of methyltrichlorosilane. Each of the resulting reaction mixtures was filtered and the filtrate was stripped of toluene, to obtain a silane containing silicon-bonded oxime groups. The yields in grams and percentages based on the halogenosilane are shown in the same table, accompanied by the molecular formula of each reaction product as identified by the same examination procedures as in Example 1, i.e., by infrared absorption spectroscopy, nuclear magnetic resonance and elementary analysis.
Table I______________________________________Test Amount of Halo- YieldNo. Halogenosilane genosilane, used of Product______________________________________ (g) (mole) (g) (%)1. Vinyltri- 48.4 0.30 92.1 98 chlorosilane2. Phenyltri- 63.5 0.30 108.0 99 chlorosilane3. Methylphenyl- 95.6 0.50 141.8 97 dichlorosilane4. Dimethyldi- 109.0 0.50 110.5 96 bromosilane5. Dimethyldi- 156.0 0.50 111.7 97 iodosilane______________________________________Formula of Product Obtained by Each Test: ##STR5## ##STR6## ##STR7## ##STR8## ##STR9##______________________________________
example 3
procedures similar to that of Example 1 were repeated with the alteration that the various halogenosilanes in varied amounts each corresponding to 0.3 mole as indicated in Table II instead of methyltrichlorosilane. Each of the resulting reaction mixtures was filtered and the filtrate was stripped of toluene, to obtain a silane expressed by formula in the same table as identified by the same examination procedures as in Example 1.
Table II__________________________________________________________________________ Amount ofTest Halogeno-No. Halogenosilane silane, used Formula of Product__________________________________________________________________________ (g)6 Ethyltri- chlorosilane 49.0 ##STR10##7 Isopropyltri- chlorosilane 53.2 ##STR11##8 Benzyltri- chlorosilane 67.5 ##STR12##9 p-Chlorophenyl- trichlorosilane 73.2 ##STR13##10 p-Cyanophenyl- trichlorosilane 70.9 ##STR14##__________________________________________________________________________
example 4
procedures similar to that of Example 1 were repeated with the alterations that the various halogenosilanes in varied amounts and the various solvents as indicated in Table III were employed instead of methyltrichlorosilane and toluene, respectively. Each of the resulting reaction mixtures was filtered and the filtrate was stripped of the solvent, to obtain a silane containing silicon-bonded oxime groups. The yields of the products obtained are given in the table in grams and in percentages based on the chlorosilane, accompanied by respective formulas as identified by the same examination procedures as in Example 1.
Table III______________________________________ Amount ofTest Halogeno- Halogeno- Yield ofNo. Solvent silane silane, used Product______________________________________ (g) (Mole) (g) (%)11 Xylene Vinylmethyl- 70.5 0.50 116.3 96 dichloro- silane12 Dibutyl- Tetra- 42.5 0.25 92.2 99ether chloro- silane______________________________________Formula of Product Obtained by Each Test: ##STR15## ##STR16##______________________________________
example 5
procedures similar to that of Example 1 were repeated with the alterations that 39.1 g (1 mole) of metallic potassium and the various solvents as indicated in Table IV were employed instead of 23 g (1 mole) of metallic sodium and toluene, respectively. Each of the resulting reaction mixtures was filtered and the filtrate was stripped of the solvent, to obtain a the same oxime-containing silane as in Example 1. The yields of the products thus obtained are given in the same table in grams and in percentages based on the chlorosilane.
Table IV______________________________________TestNo. Solvent Yield of Product______________________________________ (g) (%)13 Dioxane 89.6 9914 Benzene 89.7 99______________________________________
EXAMPLE 6
Procedures similar to that of Example 1 were repeated with the alterations that the various oximes in varied amounts each corresponding to 1 mole as indicated in Table V instead of 2-butanone oxime. Each of the resulting reaction mixtures was filtered and the filtrate was stripped of toluene, to obtain a silane expressed by molecular formula as identified by the same examination procedures as in Example 1.
Table V__________________________________________________________________________Test Amount ofNo. Oxime Oxime, used Formula of Product__________________________________________________________________________ (g)15 Acetone oxime 73 ##STR17##16 Acetophenone oxime 135 ##STR18##17 Benzophenone oxime 197 ##STR19##18 Cyclohexanone oxime 113 ##STR20##19 2, 4-Dimethyl- 3-pentanone oxime 129 ##STR21##__________________________________________________________________________>what is claimed is: 1. A method for preparing an organosilane represented by the general formula
R.sub.a.sup.1 Si(ON═Y).sub.4.sub.-a
where R 1 is a monovalent hydrocarbon group selected from the class consisting of alkyl, alkenyl, aryl and aralkyl groups and halogen- or cyano-substituted groups thereof; Y is a group denoted by R 2 R 3 C═ or R 4 C═, R 2 and R 3 , which may be identical or different, having the same meaning as R 1 defined above and R 4 being a divalent group selected from alkylene groups, halogen-substituted groups thereof and a group represented by the formula ##STR22## and a is 0, 1, 2 or 3, which comprises reacting a halogenosilane represented by the general formula
R.sub.a.sup.1 SiX.sub.4.sub.-a
where R 1 and a are as defined above and X is a halogen atom with a metal oxime represented by the general formula
Y═NOM
where Y is as defined above and M is an alkali metal. 2. The method as claimed in claim 1 wherein the amounts of said halogenosilane and metal oxime are such that there is one mole or less of halogenosilane per mole of metal oxime. 3. The method as claimed in claim 1 wherein the reaction is carried out at a temperature in the range from -70° to 200° C. 4. The method as claimed in claim 1 wherein the reaction is carried out at a temperature in the range from -10° to 150° C. 5. The method as claimed in claim 1 wherein said halogenosilane is chlorine. 6. The method as claimed in claim 1 wherein said alkali metal is sodium. 7. The method as claimed in claim 1 wherein the reaction is carried out in an organic solvent. 8. The method as claimed in claim 7 wherein said organic solvent is at least one selected from the group consisting of benzene, toluene, xylene, dibutylether and dixoane. 9. The method as claimed in claim 7 wherein the reaction is carried out at a temperature ranging from room temperature to the reflux temperature of said organic solvent. 10. The method as claimed in claim 1 wherein said metal oxime is an alkali metal derivative of an oxime selected from the group consisting of 2-butanone oxime, acetone oxime, acetophenone oxime, benzophenone oxime, cyclohexanone oxime and 2,4-dimethyl-3-pentanone oxime. 11. The method as claimed in claim 1 wherein said halogenosilane is selected from the group consisting of methyltrichlorosilane, ethyltrichlorosilane, isopropyltrichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, benzyltrichlorosilane, p-chlorophenyltrichlorosilane, p-cyanophenyltrichlorosilane, methylphenyldichlorosilane, vinylmethyldichlorosilane, dimethyldibromosilane, dimethyldiiodosilane and tetrachlorosilane.
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Organosilanes containing silicon-bonded oxime groups, i.e., ketoximosilanes, are prepared by reacting an halogenosilane with an alkali metal oxime, using no acid acceptors. This method of preparation is safe from the potentiality of explosive hazards that may exist inadvertently or inherently in the conventional reaction system, and also capable of producing amine chloride-free products.
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This application is a divisional application of application Ser. No. 336,158, filed on Feb. 26, 1973, now U.S. Pat. No. 3,893,934.
BACKGROUND OF THE INVENTION
This invention relates to imaging systems, and more particularly, to improved electrostatographic developing materials, their manufacture and use.
The formation and development of images on the surface of photoconductor materials by electrostatic means is well known. The basic xerographic process, as taught by C. F. Carlson in U.S. Pat. No. 2,297,691, involves placing a uniform electrostatic charge on a photoconductive insulating layer, exposing the layer to a light-and-shadow image to dissipate the charge on the areas of the layer exposed to the light and developing the resulting electrostatic latent image by depositing on the image a finely divided electroscopic material referred to in the art as "toner." The toner will normally be attracted to those areas of the layer which retain a charge, thereby forming a toner image corresponding to the electrostatic latent image. This powder image may then be transferred to a support surface such as paper. The transferred image may subsequently be permanently affixed to the support surface as by heat. Instead of latent image formation by uniformly charging the photoconductive layer and then exposing the layer to a light-and-shadow image, one may form the latent image by directly charging the layer in image configuration. The powder image may be fixed to the photoconductive layer if elimination of the powder image transfer step is desired. Other suitable fixing means such as solvent or overcoating treatment may be substituted for the foregoing heat fixing steps.
Several methods are known for applying the electroscopic particles to the electrostatic latent image to be developed. One development method, as disclosed by E. N. Wise in U.S. Pat. No. 2,618,552, is known as "cascade" development. In this method, a developer material comprising relatively large carrier particles having finely divided toner particles electrostatically coated thereon is conveyed to and rolled or cascaded across the electrostatic latent image bearing surface. The composition of the carrier particles is so selected as to triboelectrically charge the toner particles to the desired polarity. As the mixture cascades or rolls across the image bearing surface, the toner particles are electrostatically deposited and secured to the charged portion of the latent image and are not deposited on the uncharged or background portions of the image. Most of the toner particles accidentally deposited in the background are removed by the rolling carrier, due apparently, to the greater electrostatic attraction between the toner and the carrier than between the toner and the discharged background. The carrier and excess toner are then recycled. This technique is extremely good for the development of line copy images.
Another method of developing electrostatic images is the "magnetic brush" process as disclosed, for example, in U.S. Pat. No. 2,874,063. In this method, a developer material containing toner and magnetic carrier particles are carried by a magnet. The magnetic field of the magnet causes alignment of the magnetic carrier into a brush-like configuration. This "magnetic brush" is engaged with the electrostatic image-bearing surface and the toner particles are drawn from the brush to the latent image by electrostatic attraction.
Still another technique for developing electrostatic latent images is the "powder cloud" process as disclosed, for example, by C. F. Carlson in U.S. Pat. No. 2,221,776. In this method a developer material comprising electrically charged toner particles in a gaseous fluid is passed adjacent the surface bearing the electrostatic latent image. The toner particles are drawn by electrostatic attraction from the gas to the latent image. This process is particularly useful in continuous tone development.
Other development methods such as "touchdown" development, as disclosed by R. W. Gondlach in U.S. Pat. No. 3,166,432, may be used where suitable.
The developed image can then be read or permanently affixed to the imaging surface of the photoconductive substrate if this imaging surface is not to be reused. In the event that the imaging surface is of a reusable material and is to be used in preparation of subsequent electrostatographic copies, the developed image can be transferred to another substrate, such as paper, and then permanently affixed thereto. Various techniques have been devised to permanently affix this toner image to its substrate including overcoating the toner image with a transparent film, and solvent or thermal fusion of the tone particles to the substrate material. The energy requirements involved in thermal fixation of the toner are considerable since these thermoplastic toner materials often require temperatures in the range of 350°-400° F and higher to fuse them to the substrate. Thus, a substantial reduction in the fusion temperatures of the toner would result in a corresponding reduction in energy requirements of such an imaging process. Any reduction in the fusion temperature of the toner would also permit lowering the operating temperatures within the copier and, therefore, reduce the demands placed upon the temperature control unit within such an apparatus.
Although some of the foregoing development techniques are employed commercially today, the most widely used commercial electrostatographic development technique is the technique known as "cascade" development. A general purpose office copying machine incorporating this development process is described in U.S. Pat. No. 3,099,943. The cascade technique is generally carried out in a commercial apparatus by cascading a developer mixture over the upper surface of an electrostatic latent image-bearing drum having a horizontal axis. The developer is transported from a trough or sump to the upper portion of the drum by means of an endless belt conveyor. The developer is cascaded downward along a portion of the surface of the drum into the sump and is subsequently recycled through the developing system to develop additional electrostatic latent images. Small quantities of toner are periodically added to the developing mixture to compensate for the toner depleted by development. This process is then repeated for each copy produced by the machine and is ordinarily repeated many thousands of times during the usable life of the developer.
Thus, it is apparent from the description presented above, as well as in other development techniques, that the toner is subjected to mechanical attrition which tends to break down the particles into undesirable dust fines. Toner fines are detrimental to machine operation because they are extremely difficult to remove from reusable imaging surfaces and also because they tend to drift to other parts of the machine and deposit on critical machine parts such as optical lenses. The formation of fines is retarded when the toner contains a tough, high molecular weight resin which is capable of withstanding the shear and impact forces imparted to the toner in the machine. Unfortunately, many high molecular weight materials cannot be employed in high speed automatic machines because they cannot be rapidly fused during a powder image heat fixing step. Attempts to rapidly fuse a high melting point toner by means of oversized high capacity heating units have been confronted with the problems of preventing the charring of paper receiving sheets and of adequately dissipating the heat evolved from the fusing unit or units. Thus, in order to avoid charring or combustion, additional equipment such as complex and expensive cooling units are necessary to properly dispose of the large quantity of heat generated by the fuser. Incomplete removal of the heat evolved will result in operator discomfort and damage to heat-sensitive machine components. Further, the increased space occupied by and the high operating cost of the heating and cooling units, often outweigh the advantages achieved by the increased machine speed. On the other hand; low molecular weight resins which are easily heat fused at relatively low temperatures are often undesirable because these materials tend to form thick films on reusable photoconductor surfaces. These films tend to cause image degradation and contribute to machine maintenance down time. In addition, low molecular weight resins tend to form tacky images on the copy sheet which often offset to other adjacent sheets. Further, toner particles containing low molecular weight resins tend to bridge, cake, and block in the shipping container as well as in the xerographic machine. Also, the toner material must be capable of accepting a charge of the correct polarity when brought into rubbing contact with the surface of carrier materials in cascade, magnetic brush or touch-down development systems. Some resinous materials which possess many properties which would be desirable in xerographic toners dispense poorly and cannot be used in automatic copying and duplicating machines. Other resins dispense well but form images which are characterized by low density, poor resolution, or high background. Further, some resins are unsuitable for processes where electrostatic transfer is employed. Many thermoplastic materials, such as those presently in use in electrostatographic toners, have traditionally been difficult to mold or form because of unfavorable rheological properties. probably the most widely accepted technique for modification of these thermoplastics to facilitate forming of such materials has been the inclusion of certain additives in said materials designed to reduce their melt viscosity. These additives, generally referred to in the art as "plasticizers", include non-volatile organic liquids or low melting solids, e.g. phthalate, adipate and sebacate esters and aryl phosphate esters.
The interaction of the plasticizer and the resin in the melt results in a marked improvement in the composition's rheological properties by affecting a shift in both the glass transition temperature and fusion points of the composition to lower temperatures. This shift in the glass transition temperature of the thermoplastic materials used as electrostatographic toners, is substantial, can cause these discrete, finely-divided toner particles to form larger agglomerates. This agglomeration, more commonly referred to in the electrostatographic art as "blocking", adversely affects the free flow characteristics of the toner. For example, in cascade-type development systems, the momentum of these larger toner particles as they tumble over the imaging member can exceed the attractive forces of the latent image and, therefore, result in failure of development of the latent image by these larger toner particles. Since most thermoplastic materials are deficient in one or more of the above areas, there is a continuing need for improved toners and developers.
SUMMARY OF THE INVENTION
It is, therefore, an object of this invention to provide a toner overcoming the above noted deficiencies.
It is another object of this invention to provide a toner which is resistant to film formation when employed in conventional xerographic copying and duplicating devices.
It is another object of this invention to provide a xerographic toner which forms images having reduced background.
It is another object of this invention to provide a free flowing toner which is resistant to agglomeration.
It is another object of this invention to provide a xerographic toner which can be fused at higher rates with less heat energy.
It is another object of this invention to provide a xerographic toner which forms high resolution images.
It is another object of this invention to provide a xerographic toner which is resistant to mechanical attrition during the development process.
It is another object of this invention to provide a xerographic toner having improved dispensing characteristics.
It is another object of this invention to provide a modified toner composition which has a fusion temperature substantially less than that of its unmodified counterpart and which yet remains relatively unchanged with respect to its glass transition temperature.
It is another object of this invention to provide improved imaging processes employing one of the modified toner compositions of this invention.
It is another object of this invention to provide a toner and developer having physical and chemical properties superior to those of known toners and developers.
The above objects and others are accomplished by providing a finely-divided low melting toner comprising a colorant, a thermoplastic resin comprising a vinyl resin, and at least one arylsufonamide formaldehyde adduct having the general structure ##STR1## wherein R 1 and R 2 are either hydrogen or methyl provided that where R 1 or R 2 is methyl, the other is hydrogen.
This invention also embraces imaging processes in which said improved toner compositions are employed and a method for the reduction of the fusion temperature of thermoplastic materials, while at the same time having such materials remain relatively unchanged with respect to their glass transition temperature.
For optimum operation in high speed electrostatographic machines employing paper receiving webs, the toner should have a melting range between about 110° F to about 300° F and a melt viscosity of less than about 2.0 × 10 - 4 poise up to temperatures of about 300° F. Toner melting temperatures below about 300° F are preferred because heat dissipation and paper degradation problems are avoided. The developers of this invention containing said improved toner compositions are characterized by outstanding fusing rates, high cleanability from electrostatic imaging surfaces, greater triboelectric stability, denser toner images, and increased resistance to mechanical attrition. Unexpectedly, both the fire hazard and excessive power consumption problems encountered in high speed electrostatographic development processes are obviated when toners containing the above-described arylsulfonamide formaldehyde adducts are employed.
Any suitable vinyl resin having a melting point of at least about 110° F may be employed in the toners of this invention. The vinyl resin may be a homopolymer or a copolymer of two or more vinyl monomers. Typical monomeric units which may be employed to form vinyl polymers include: styrene, p-chlorostyrene; vinyl naphthalene; ethylenically unsaturated mono-olefins such as ethylene, propylene, butylene, isobutylene and the like; vinyl esters such as vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate and the like; esters of alphamethylene aliphatic monocarboxylic acids such as methyl acrylate, ethyl acrylate, n-butylacrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2 chloroethyl acrylate, phenyl acrylate, methyl-alpha-chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like; acrylonitrile, methacrylonitrile, acrylamide, vinyl ethers such as vinyl methyl ether, vinyl isobutyl ether, vinyl ethyl ether, and the like; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone and the like; vinylidene halides such as vinylidene chloride, vinylidene chlorofluoride and the like; and N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidene and the like; and mixtures thereof. Generally, suitable vinyl resins employed in the toner have a weight average molecular weight between about 3,000 to about 500,000.
Toner resins containing relatively high percentages of a styrene resin are preferred. The presence of a styrene resin is preferred because a greater degree of image definition is achieved with a given quantity of adduct material. Further, denser images are obtained when at least about 25 percent by weight, based on the total weight of resin in the toner, of a styrene resin is present in the toner. The styrene resin may be a homopolymer of styrene or styrene homologues or copolymers of styrene with other monomeric groups containing a single methylene group attached to a carbon atom by a double bond. Thus, typical monometric materials which may be copolymerized with styrene by addition polymerization include: p-chlorostyrene; vinyl naphthalene; ethylenically unsaturated mono-olefins such as ethylene, propylene, butylene, isobutylene and the like; vinyl esters such as vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate and the like; esters of alpha-methylene aliphatic monocarboxylic acids such as methyl acrylate, ethyl acrylate, n-butylacrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate phenyl acrylate, methyl-alpha-chloroacrylate methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like; acrylonitrile, methacrylonitrile, acrylamide, vinyl ethers such as vinyl methyl ether, vinyl isobutyl ether, vinyl ethyl ether, and the like, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone and the like; vinylidene halides such as vinylidene chloride, vinylidene chlorofluoride and the like; and N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidene and the like; and mixtures thereof. The styrene resins may also be formed by the polymerization of mixtures of two or more of these unsaturated monomeric materials with a styrene monomer. The expression "addition polymerization" is intended to include known polymerization techniques such as free radical, anionic and cationic polymerization processes.
The vinyl resins, including styrene type resins, may also be blended with one or more other resins if desired. When the vinyl resin is blended with another resin, the added resin is preferably another vinyl resin because the resulting blend is characterized by especially good triboelectric stability and uniform resistance against physical degradation. The vinyl resins employed for blending with the styrene type or other vinyl resin may be prepared by the addition polymerization of any suitable vinyl monomer such as the vinyl monomers described above. Other thermoplastic resins may also be blended with the vinyl resins of this invention. Typical non-vinyl type thermoplastic resins include: rosin modified phenol formaldehyde resins, oil modified epoxy resins, polyurethane resins, cellulosic resins, polyether resins and mixtures thereof. When the resin component of the toner contains styrene copolymerized with another unsaturated monomer or a blend of polystyrene and another resin, a styrene component of at least about 25 percent by weight based on the total weight of the resin present in the toner is preferred because denser images are obtained and a greater degree of image definition is achieved with a given quantity of adduct material.
The combination of the resin component, colorant, and adduct, whether the resin component is a homopolymer, copolymer, or blend, should have a blocking temperature of at least about 110° F and a melt vicosity of less than about 2.5 × 10 - 4 poise temperatures up to about 450° F. When the toner is characterized by a blocking temperature less than about 110° F, the toner particles tend to agglomerate during storage and machine operation and also form undesirable films on the surface of reusable photoreceptors which adversely affect image quality. If the melt viscosity of the toner is greater than about 2.5 × 10 - 4 poise at temperatures above about 450°F, the toner material of this invention generally does not adhere properly to a receiving sheet even under conventional electrostatographic machine fusing conditions and may easily be removed by rubbing.
The arylsulfonamide formaldehyde adducts in the preferred embodiments of this invention may be selected from the 2- methylbenzene sulfonamide formaldehyde adduct, the 4-methylbenzene sulfonamide formaldehyde adduct, and mixtures thereof. In addition, suitable sulfonamide formaldehyde adducts may be derived from N-cyclohexyl p-toluene sulfonamide, N-ethyl p-toluene sulfonamide, o-toluene sulfonamide, p-toluene sulfonamide, N,N-di-p-hydroxyethyl- p-toluene sulfonamide, N,N-dimethyl benzene sulfonamide, N-cyclohexyl benzene sulfonamide, N-cyclohexyl-3,4-dichlorobenzene sulfonamide, N-allyl p-toluene sulfonamide, N,N-di-p-hydroxyethyl p-toluene sulfonamide, N-cyclohexyl p-toluene sulfonamide and the like. These adducts are formed by condensation of arylsulfonamides with formaldehyde and generally have a melting point between about 50° F and about 250° F. Some of these adducts are sold under the "Santolite" trademark by the Monsanto Company, St. Louis, Missouri, for example, Santolite MHP and Santolite MS-80%. Generally, the adduct is employed in an amount from about 5 percent to about 55 percent by weight based on the total weight of the resinous component of the toner. Preferably, the adduct is employed in an amount from about 10 percent to about 40 percent by weight based on the total weight of the resinous component of the toner because as the relative quantity of adduct in the toner is increased above about 60 percent, the mechanical strength, creep resistance, and permanency of the ultimate fused toner image begins to decrease rapidly. Thus, when brittle, non-polymeric compounds such as the compounds disclosed in U.S. Pat. No. 3,272,644 are employed in automatic copying and duplicating machines, extensive toner dust is formed and the fused toner images tend to crumble and flake off receiving sheets when the sheets are folded. Further, some solid non-polymeric materials tend to vaporize or sublime and form toxic or flammable fumes. When less than about 3 percent of the adduct is employed in the toner, the toner fusing, flow, and triboelectric properties are substantially the same as a toner which does not contain the adduct. If desired, mixtures of adduct may be employed in the toner. An increase in the relative quantity of adduct tends to reduce the melt viscosity of the ultimate toner. It has been found that the fusing point of toner compositions is generally correlative with the melt viscosity of polymer-toner compositions. In accordance with this invention, the melt viscosity of a polymer-toner composition may be lowered by the addition of a relatively low melting arylsulfonamide formaldehyde adduct thereto wherein said adduct does not significantly affect the glass transition temperature of the polymer-toner composition and hence the blocking temperature of the toner is not influenced. Thus, due to the substantial reduction in the fusion temperature of the toner compositions of this invention, imaging processes employing said toner compositions will have markedly reduced energy requirements with respect to the thermal fixation of developed toner images. In addition, the maintenance of relatively constant glass transition temperatures in said toner compositions also prevents agglomeration or "blocking" of the discrete, finely-divided toner particles in developer reservoirs. Although Applicant does not wish to be bound by any theory for the unexpected findings of this invention, it is hypothesized that that there may be two possible mechanisms for the results discovered. It is initially envisioned that the arylsulfonamide formaldehyde adduct functions as a solvent for the polymer-toner in the liquid state at elevated temperature but not in the solid state at ambient temperature. Alternatively, the adduct above its melting point and above the glass transition temperature of the toner resin permits sufficient deformation of the polymer to permit fixation at lower temperatures.
It is to be understood that the specific formulas given for the units contained in the adducts and resins of this invention represent the vast majority of the units present, but do not exclude the presence of other monomeric units or reactants than those which have been shown. For example, some commercial materials such as polystyrenes, and polychlorinated polyphenyl compounds contain trace amounts of homologues or unreacted or partially reacted monomers. Any minor amount of such substituents may be present in the materials of this invention.
Any suitable pigment or dye may be employed as the colorant for the toner particles. Toner colorants are well known and include, for example, carbon black, nigrosine dye, aniline blue, Calco Oil Blue, chrome yellow, ultra marine blue, duPont Oil Red, Quinoline Yellow, methylene blue chloride, phthalocyanine blue, Malachite Green Oxalate, lamp black, Rose Bengal and mixtures thereof. The pigment or dyes should be present in the toner in a sufficient quantity to render it highly colored so that it will form a clearly visible image on a recording member. Thus, for example, where conventional electrostatographic copies of typed documents are desired, the toner may comprise a black pigment such as carbon black or a black dye such as Amaplast Black dye, available from the National Aniline Products, Inc. Generally, the pigment is employed in an amount from about 1 percent to about 20 percent by weight based on the total weight of the colored toner. If the toner colorant employed is a dye, substantially smaller quantities of colorant may be used. However, since a number of the above pigments used in electrostatographic toner compositions may affect both the glass transition and fusion temperatures of the toner compositions of this invention, their concentration preferably should not exceed about 10 percent by weight of the colored toner.
The toner compositions of the present invention may be prepared by any well-known toner mixing and comminution technique. For example, the ingredients may be thoroughly mixed by blending, mixing and milling the components and thereafter micropulverizing the resulting mixture. Another well-known technique for forming toner particles is to spray-dry a ball-milled toner composition comprising a colorant, a resin, and a solvent.
Generally, the degree of quality of toner fix at a given fuser temperature decreases with an increase in toner melt vicosity. As discussed above, if the melt viscosity of the toners of this invention is greater than about 2.5 × 10 - 4 poise at temperatures above about 450°F, the toner materials do not adhere properly to a receiving sheet even under conventional electrostatographic machine fusing conditions. Thus, the melt viscosity value of the toners of this invention aids in the determination of the degree of flow and penetration of the toner into the surface of a receiving substrate such as paper during the heat fixing step. The expression "melt viscosity", as employed herein, is a measure of the ratio of shear stress to shear rate in poise at a given temperature. All viscosity measurements are determined using a Ferronti-Shirley Cone Anol Plate Viscometer.
When the toner mixtures of this invention are to be employed in a cascade development process, the toner should have an average particle size less than about 30 microns and preferably between about 4 and about 20 microns for optimum results. For use in powder cloud development methods, particle diameters of slightly less than 1 micron are preferred.
Suitable coated and uncoated carrier materials for cascade development are well known in the art. The carrier particles comprise any suitable solid material, provided that the carrier particles acquire a charge having an opposite polarity to that of the toner particles when brought in close contact with the toner particles so that the toner particles adhere to and surround the carrier particles. When a positive reproduction of the electrostatic images is desired, the carrier particle is selected so that the toner particles acquire a charge having a polarity opposite to that of the electrostatic image. Alternatively if a reversal reproduction of the electrostatic image is desired, the carrier is selected so that the toner particles acquire a charge having the same polarity as that of the electrostatic image. Thus, the materials for the carrier particles are selected in accordance with their triboelectric properties in respect to the electroscopic toner so that when mixed or brought into mutual contact, one component of the developer is charged positively if the other component is below the first component in the triboelectric series and negatively if the other component is above the first component in a triboelectric series. By proper selection of materials in accordance with their triboelectric effects, the polarities of their charge, when mixed, are such that the electroscopic toner particles adhere to and are coated on the surfaces of carrier particles and also adhere to that portion of the electrostatic image-bearing surface having a greater attraction for the toner than the carrier particles. Typical carriers include sodium chloride, ammonium chloride, aluminum potassium chloride, Rochelle salt, sodium nitrate, aluminum nitrate, potassium chlorate, granular zircon, granular silicon, methyl methacrylate, glass, silicon dioxide, nickel, steel, iron, ferrites, and the like. The carriers may be employed with or without a coating. Many of the foregoing and other typical carriers are described by L. E. Walkup et al. in U.S. Pat. No. 2,638,416 and E. N. Wise in U.S. Pat. No. 2,618,552. An ultimate coated carrier particle diameter between about 50 microns to about 1,000 microns is preferred because the carrier particles then possess sufficient density and inertia to avoid adherence to the electrostatic images during the cascade development process. Adherence of carrier beads to electrostatographic drums is undesirable because of the formation of deep scratches on the surface during the imaging transfer and drum cleaning steps, particularly where cleaning is accomplished by a web cleaner such as the web disclosed by W. P. Graff, Jr., et al. in U.S. Pat. No. 3,186,838. Also print deletion occurs when carrier beads adhere to electrostatographic imaging surfaces. Generally speaking, satisfactory results are obtained when about 1 part toner is used with about 10 to 200 parts by weight of carrier.
The toner compositions of the instant invention may be employed to develop electrostatic latent images on any suitable electrostatic latent image-bearing surface including conventional photoconductive surfaces. Well-known photoconductive materials include vitreous selenium, organic or inorganic photoconductors embedded in a non-photoconductive matrix, organic or inorganic photoconductors embedded in a photoconductive matrix, or the like. Representative patents in which photoconductive materials are disclosed include U.S. Pat. No. 2,803,542 to Ullrich, U.S. Pat. No. 2,970,906 to Bixby, U.S. Pat. No. 3,121,006 to Middleton, U.S. Pat. No. 3,121,007 to Middleton, and U.S. Pat. No. 3,151,982 to Corrsin.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following examples further define, describe, and compare methods of preparing the toner materials of the present invention and of utilizing them to develop electrostatic latent images. Parts and percentages are by weight unless otherwise indicated.
EXAMPLE I
A control sample of about 1 part of a conventional toner composition comprising a mixture of styrene/n-butyl methacrylate copolymer, polyvinyl butyral, and carbon black as the colorant as disclosed in U.S. Pat. No. 3,079,342 is mixed with about 99 parts by weight of coated carrier beads as disclosed in U.S. Pat. No. 3,526,533 to form a developer mixture. The toner has a blocking temperature of about 130° F. Copies of a standard test pattern are made with the developer mixture in a modified Xerox 3600-III copying machine which are then passed through a standard Xerox 4000 fuser unit mounted externally to the Xerox 3600-III machine. The fuser temperature is regulated with a proportional temperature controller and is monitored by means of a thermocouple wherein the fuser temperature is varied in 10° F increments to determine the fix temperature for minimum acceptable fix and hot offset. The minimum fix level is established at 10 ± 2 "Taber Cycles". The term "Taber Cycles" represents the degree of fix obtained using a test method based on the resistance of a fixed toner image to abrasion with a Taber Abrader, Model 174, available from Welch Scientific Co. After passage through the fuser, the copy sheets are mounted on a specimen card having a diameter of about 4.25 inches and abraded using a standard CS-10 test wheel. The number of cycles required to result in about a 20 percent decrease in image density is recorded. A minimum fuser temperature is established when about a 20 percent decrease in image density is observed. Generally, an abrasion run of 10 ± 2 revolutions of the abrading wheel constitutes acceptable fusing. The minimum fuser temperature at which legible copies are obtained with this toner is found to be about 380° F. The maximum fuser temperature at which hot offset to the fuser roll occurs is found to be about 430° F.
EXAMPLE II
A toner composition is prepared comprising about 81 parts by weight of a copolymer of about 65 parts by weight of styrene and 35 parts by weight of butyl methacrylate, about 9 parts by weight of carbon black (Neo Spectra Mark II, available from Columbian Carbon Co.), and about 10 parts by weight of arylsulfonamide formaldehyde adduct (Santolite MHP, available from Monsanto Co.). After melting and preliminary mixing, the toner composition is fed to a rubber mill and thoroughly milled to yield a uniformly dispersed composition of the carbon black in the resin body. The resulting mixture is then cooled and finely subdivided in a jet pulverizer to yield toner particles having an average particle size ranging between about 10 to about 20 microns. The toner has a blocking temperature of about 130° F. About 1 part of the pulverized toner particles are mixed with about 99 parts by weight of the carrier beads of Example I and substituted for the developer in the testing machine described in Example I. Under substantially identical test conditions, it is found that the minimum fuser temperature at which legible copies are obtained with this toner is about 325° F. The maximum fuser temperature at which hot offset to the fuser roll occurs is found to be about 410° F. These results clearly indicate that this toner enables a reduction of about 55° F from the fuser temperature required for the control sample of Example I. The toner dispenses well and high resolution images substantially free from background are obtained.
EXAMPLE III
A toner composition is prepared comprising about 71 parts by weight of copolymer of about 65 parts by weight of styrene and 35 parts by weight of butyl methacrylate, about 9 parts by weight of carbon black (Neo Spectra Mark II, available from Columbian Carbon Co.), and about 20 parts by weight of arylsulfonamide formaldehyde adduct (Santolite MHP, available from Monsanto Co.). After melting and preliminary mixing, the toner composition is fed to a rubber mill and thoroughly milled to yield a uniformly dispersed composition of the carbon black in the resin body. The resulting mixture is then cooled and finely subdivided in a jet pulverizer to yield toner particles having an average particle size ranging between about 10 to about 20 microns. The toner has a blocking temperature of about 130° F. About 1 part of the pulverized toner particles are mixed with about 99 parts by weight of the carrier beads of Example I and substituted for the developer in the testing machine described in Example I. Under substantially identical test conditions, it is found that the minimum fuser temperature at which legible copies are obtained with this toner is about 315° F. The maximum fuser temperature at which hot offset to the fuser roll occurs is found to be about 410° F. These results clearly indicate that this toner enables a reduction of about 65° F from the fuser temperature required for the control sample of Example I. The toner dispenses well and high resolution images substantially free from background are obtained.
EXAMPLE IV
A toner composition is prepared comprising about 61 parts by weight of a copolymer of about 65 parts by weight of styrene and 35 parts by weight of butyl methacrylate, about 9 parts by weight of carbon black (Neo Spectra Mark II, available from Columbian Carbon Co.), and about 30 parts by weight of arylsulfonamide formaldehyde adduct (Santolite MHP, available from Monsanto Co.). After melting and preliminary mixing, the toner composition is fed to a rubber mill and thoroughly milled to yield a uniformly dispersed composition of the carbon black in the resin body. The resulting mixture is then cooled and finely subdivided in a jet pulverizer to yield toner particles having an average particle size ranging between about 10 to about 20 microns. The toner has a blocking temperature of about 130° F. About 1 part of the pulverized toner particles are mixed with about 99 parts by weight of the carrier beads of Example I and substituted for the developer in the testing machine described in Example I. Under substantially identical test conditions, it is found that the minimum fuser temperature at which legible copies are obtained with this toner is about 310° F. The maximum fuser temperature at which hot offset to the fuser roll occurs is found to be about 405° F. These results clearly indicate that this toner enables a reduction of about 70° F from the fuser temperature required for the control sample of Example I. The toner dispenses well and high resolution images substantially free from background are obtained.
EXAMPLE V
A toner composition is prepared comprising about 51 parts by weight of a copolymer of about 65 parts by weight of styrene and 35 parts by weight of butyl methacrylate, about 9 parts by weight of carbon black (Neo Spectra Mark II, available from Columbian Carbon Co.), and about 40 parts by weight of arylsulfonamide formaldehyde adduct (Santolite MHP, available from Monsanto Co.). After melting and preliminary mixing, the toner composition is fed to a rubber mill and thoroughly milled to yield a uniformly dispersed composition of the carbon black in the resin body. The resulting mixture is then cooled and finely subdivided in a jet pulverizer to yield toner particles having an average particle size ranging between about 10 to about 20 microns. The toner has a blocking temperature of about 130° F. About 1 part of the pulverized toner particles are mixed with about 99 parts by weight of the carrier beads of Example I and substituted for the developer in the testing machine described in Example I. Under substantially identical test conditions, it is found that the minimum fuser temperature at which legible copies are obtained with this toner is about 300° F. The maximum fuser temperature at which hot offset to the fuser roll occurs is found to be about 390° F. These results clearly indicate that this toner enables a reduction of about 80° F from the fuser temperature required for the control sample of Example I. The toner dispenses well and high resolution images substantially free from background are obtained.
EXAMPLE VI
A control toner composition is prepared comprising about 91 parts by weight of a copolymer of about 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate and about 9 parts by weight of carbon black (Black Pearls L, available from Cabot Corp., Boston, Mass.). After melting and preliminary mixing, the toner composition is fed to a rubber mill and thoroughly milled to yield a uniformly dispersed composition of the carbon black in the resin body. The resulting mixture is then cooled and finely subdivided in a jet pulverizer to yield toner particles having an average particle size ranging between about 10 to about 20 microns. The toner has a blocking temperature of about 140° F. About 1 part of the pulverized toner particles are mixed with about 99 parts by weight of the carrier beads of Example I and substituted for the developer in the testing machine described in Example I. Under substantially identical test conditions, it is found that the minimum fuser temperature at which legible copies are obtained with this toner is about 400° F. The maximum fuser temperature at which hot offset to the fuser roll occurs is found to be about 460° F.
EXAMPLE VII
A toner composition is prepared comprising about 81 parts by weight of a copolymer of about 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate, about 9 parts by weight of carbon black (Black Pearls L, available from Cabot Corp., Boston, Mass.), and about 10 parts by weight of arylsulfonamide formaldehyde adduct (Santolite MHP, available from Monsanto Co.). After melting and preliminary mixing, the toner composition is fed to a rubber mill and thoroughly milled to yield a uniformly dispersed composition of the carbon black in the resin body. The resulting mixture is then cooled and finely subdivided in a jet pulverizer to yield toner particles having an average particle size ranging between about 10 to about 20 microns. The toner has a blocking temperature of about 140° F. About 1 part of the pulverized toner particles are mixed with about 99 parts by weight of the carrier beads of Example I and substituted for the developer in the testing machine described in Example I. Under substantially identical test conditions, it is found that the minimum fuser temperature at which legible copies are obtained with this toner is about 340° F. The maximum fuser temperature at which hot offset to the fuser roll occurs is found to be about 430° F. These results clearly indicate that this toner enables a reduction of about 60° F from the fuser temperature required for the control sample of Example VI. The toner dispenses well and high resolution images substantially free from background are obtained.
EXAMPLE VIII
A toner composition is prepared comprising about 71 parts by weight of a copolymer of about 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate, about 9 parts by weight of carbon black (Black Pearls L, available from Cabot Corp., Boston, Mass.), and about 20 parts by weight of arylsulfonamide formaldehyde adduct (Santolite MHP, available from Monsanto Co.). After melting and preliminary mixing, the toner composition is fed to a rubber mill and thoroughly milled to yield a uniformly dispersed composition of the carbon black in the resin body. The resulting mixture is then cooled and finely subdivided in a jet pulverizer to yield toner particles having an average particle size ranging between about 10 to about 20 microns. The toner has a blocking temperature of about 140° F. About 1 part of the pulverized toner particles are mixed with about 99 parts by weight of the carrier beads of Example I and substituted for the developer in the testing machine described in Example I. Under substantially identical test conditions, it is found that the minimum fuser temperature at which legible copies are obtained with this toner is about 330° F. The maximum fuser, temperature at which hot offset to the fuser roll occurs is found to be about 420° F. These results clearly indicate that this toner enables a reduction of about 70° F from the fuser temperature required for the control sample of Example VI. The toner dispenses well and high resolution images substantially free from background are obtained.
EXAMPLE IX
A toner composition is prepared comprising about 61 parts by weight of a copolymer of about 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate, about 9 parts by weight of carbon black (Black Pearls L, available from Cabot Corp., Boston, Mass.), and about 30 parts by weight of arylsulfonamide formaldehyde adduct (Santolite MHP, available from Monsanto Co.). After melting and preliminary mixing, the toner composition is fed to a rubber mill and thoroughly milled to yield a uniformly dispersed composition of the carbon black in the resin body. The resulting mixture is then cooled and finely subdivided in a jet pulverizer to yield toner particles having an average particle size ranging between about 10 to about 20 microns. The toner has a blocking temperature of about 140° F. About 1 part of the pulverized toner particles are mixed with about 99 parts by weight of the carrier beads of Example I and substituted for the developer in the testing machine described in Example I. Under substantially identical test conditions, it is found that the minimum fuser temperature at which legible copies are obtained with this toner is about 320° F. The maximum fuser temperature at which hot offset to the fuser roll occurs is found to be about 410° F. These results clearly indicate that this toner enables a reduction of about 80° F from the fuser temperature required for the control sample of Example VI. The toner dispenses well and high resolution images substantially free from background are obtained.
EXAMPLE X
A toner composition is prepared comprising about 51 parts by weight of a copolymer of about 80 parts by weight of styrene and 20 parts by weight of isobutyl methacrylate, about 9 parts by weight of carbon black (Black Pearls L, available from Cabot Corp., Boston, Mass.), and about 40 parts by weight of arylsulfonamide formaldehyde adduct (Santolite MHP, available from Monsanto Co.). After melting and preliminary mixing, the toner composition is fed to a rubber mill and thoroughly milled to yield a uniformly dispersed composition of the carbon black in the resin body. The resulting mixture is then cooled and finely subdivided in a jet pulverizer to yield toner particles having an average particle size ranging between about 10 to about 20 microns. The toner has a blocking temperature of about 140° F. About 1 part of the pulverized toner particles are mixed with about 99 parts by weight of the carrier beads of Example I and substituted for the developer in the testing machine described in Example I. Under substantially identical test conditions, it is found that the minimum fuser temperature at which legible copies are obtained with this toner is about 310° F. The maximum fuser temperature at which hot offset to the fuser roll occurs is found to be about 400° F. These results clearly indicate that this toner enables a reduction of about 90° F from the fuser temperature required for the control sample of Example VI. The toner dispenses well and high resolution images substantially free from background are obtained.
EXAMPLE XI
Samples of the developer compositions of Examples I-V are employed in the copying machine described in Example I to make copies of a standard test image. The standard test patterns are printed to provide an integrated optical density as determined with a Welch Densitometer, Model 3834, of 1.2 ± 0.1. The degree of fix at various temperatures employing the fuser unit described in Example I is evaluated. The results are reported in "Taber Cycles" required to reduce the initial density by 20 percent. The results are as indicated below in Table I.
Table I______________________________________Average Taber Cycles______________________________________Temp. ° F Example 1 2 3 4 5______________________________________290 -- -- 5 7 6300 -- 3 8 8 12310 -- 5 9 12 15320 2.0 8 14 18 18330 3.0 16 17 22 21350 3.5 20 23 29 27360 4.5 24 31 37 30370 6.0 29 31 37 34380 8.0 31 33 39 38390 14.0 32 32 38 45400 17.0 40 30 35 --410 19.5 43 41 50 --420 20.5 -- -- -- --______________________________________
From the above results, it is readily apparent that the minimum acceptable fix level of 10 ± 2 Taber Cycles may be obtained with the toner compositions of this invention at a reduction of about 60° F to about 80° F. In addition, at comparable fixing temperatures, the average number of Taber Cycles obtained is significantly higher.
EXAMPLE XII
The glass transition temperature of a copolymer resin comprising about 65 parts by weight of styrene and about 35 parts by weight of butyl methacrylate was determined using a Differential Scanning Calorimeter, 10° c/min. heating rate, and 4 mcal./sec. sensitivity. Measurements were made in a flowing Nitrogen atmosphere and the dial temperatures were converted for thermal lag using the melting point of those crystalline substances as references (octadecone, naphthalene, and p-nitrotoluene). The glass transition temperature of the aforementioned copolymer resin was found to be about 56.6° C. After mixing about 10 parts by weight and about 25 parts by weight, respectively, of an arylsulfonamide formaldehyde adduct (Santolite MHP) based on the total weight of the mixture with the aforementioned copolymer resin, the glass transition temperature of the mixtures was found to be about 58.9° C and 57.5° C, respectively, indicating within experimental error that the addition of the adduct does not significantly affect the glass transition temperature of the copolymer resin and hence the blocking temperature of such a resin-based toner composition is not adversely influenced.
EXAMPLE XIII
The melt viscosity of a copolymer resin comprising about 65 parts by weight of styrene and about 35 parts by weight of butyl methacrylate was determined by using a Ferranti-Shirley Cone and Plate Viscometer. Data are cited at 30 sec - 1 shear rate. The melt viscosity of the aforementioned copolymer resin at various temperatures was found to be about 8.0 × 10 3 poise at 140° C; 3.6 × 10 3 poise at 150° C; 1.9 × 10 3 poise at 160° C; and 1.1 × 10 3 poise at 170° C. After mixing about 25 parts by weight of an arylsulfonamide formaldehyde adduct (Santolite MHP) with the aforementioned copolymer resin, the melt viscosity of the resultant mixture was found to be about 4.9 × 10 3 at 130° C; 2.8 × 10 3 poise at 140° C; 1.1 × 10 3 poise at 150° C; 8.2 × 10 2 poise at 160° C; and 4.1 × 10 2 poise at 170° C, respectively, indicating, within experimental error, that the addition of the adduct results in between about three to four fold lowerings of the melt viscosity of the copolymer resin. In turn, the melt viscosity change is reflected in substantially lower fusing temperatures of the toner compositions.
The expression "developer material" as employed herein is intended to include electroscopic toner material or combinations of toner material and carrier material.
Although specific materials and conditions are set forth in the foregoing examples, these are merely intended as illustration of the present invention. Various other suitable thermoplastic toner resin components, additives, colorants, and development processes such as those listed above may be substituted for those in the examples with similar results. Other materials may also be added to the toner or carrier to sensitize, synergize, or otherwise improve the fusing properties or other desirable properties of the system.
Other modifications of the present invention will occur to those skilled in the art upon a reading of the present disclosure. These are intended to be included within the scope of this invention.
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An electrostatographic imaging process comprising the steps of forming an electrostatic latent image on a surface and developing said image by contacting it with an electrostatographic developer material comprising particles, the particles including finely-divided toner material have a particle size of up to about 30 microns, a melting point of at least about 110° F, a melt viscosity of less than about 2.5 × 10.sup. -4 poise at temperatures up to about 450° F, the toner material comprising a colorant, a thermoplastic resin consisting essentially of a vinyl polymer having a melting point of at least about 110° F, and from about 5 percent to about 55 percent by weight, based on the weight of the vinyl polymer, of an arylsulfonamide formaldehyde adduct having a melting point between about 50° F and about 250° F, whereby at least a portion of the toner material is attracted to and held on the surface in conformance to the electrostatic latent image.
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This is a continuation of application Ser. No. 686,836 filed December 27, 1984, now abandoned.
BACKGROUND OF THE INVENTION
This application pertains to a new composition, which can be used in the cosmetic or pharmaceutical field, that contains vegetable extracts and which acts on the capillaries by reducing their permeability and increasing their resistance.
Extracts of Ruscus aculeatus L. which are either isolated or associated with a vitamin factor have been recommended for treatment of functional problems in connection with venous insufficiency and capillary brittleness. Also, fractions which are enriched with stabilized Ruscus aculeatus L. rhizome saponins have been described as having therapeutic activity especially with venous disorders, varicose veins, ulcers, hemorrhoids and various disorders in the capillary system such as purpura, epistaxis, chilblains or gynecological disorders.
The prior art compositions are generally described in French patent No. 77/01290 as well as in B.S.M. No. 3,994.M.
SUMMARY OF THE INVENTION
After various studies on Ruscus aculeatus L. extracts, it was found that it is possible to obtain a complementary synergy of activity in the reduction of capillary permeability and in the increase of capillary resistance, by linking Ruscus aculeatus L. extracts with sage or Salvia officinalis L. extracts. Also, by linking these extracts with passiflore or passion-flower (Passiflora incarnata) extracts the synergy of activity can be increased substantially and the activity was found to be more constant over a period of time.
Therefore, the present invention pertains to a cosmetic or pharmaceutical composition which acts on capillaries by reducing their permeability and by increasing their resistance. The composition of the present invention contains in a suitable cosmetic or pharmaceutical carrier, a combination of vegetable extracts comprising:
(i) a fragon extract (Ruscus aculeatus L.), and
(ii) a sage extract (Salvia officinalis L.).
According to the invention, this combination of vegetable extracts exists in a composition with the following concentrations, as expressed in dry matter:
______________________________________dry extract of fragon (Ruscus aculeatus L.) 0.1 to 3%and preferably 0.3 to 2.5%dry extract of sage (Salvia officina1is L.) 0.01 to 5%and preferably 0.3 to 3.5%______________________________________
According to a preferred embodiment, the composition can also contain a soft extract of passiflore (Passiflora incarnata) with a concentration (expressed as solid matter)
______________________________________of from 0.l to 2%and preferably from 0.2 to 1.5%______________________________________
The vasoprotective effect of these combinations as well as their synergy of activity were highlighted by the petechia method which will be described below.
DETAILED DESCRIPTION
The dry extract of fragon or butcher's broom (Ruscus aculeatus L.), which is used in the compositions of the present invention, is obtained from rhizomes which have been previously ground and extracted with a hydro-alcoholic solution of an alcohol containing 3 to 6 carbon atoms, and preferably with water-saturated n-butanol.
Representative extract methods are described in French patent Nos. 1,377,453, 69/23340 and 71/29817, the latter patent pertaining especially to the purification of extracts which are obtained for the purpose of enriching them with saponins.
Ruscus aculeatus L. extracts obtained from these methods appear as a tan powder which is 2% soluble in water and in alcohol at 60° C. The extracts have at least a 65% saponin content and preferably have a saponin content of from 70 to 80%.
The dry sage or Salvia officinalis L. extract is an extract that is obtained from leaves and dried flowery extremities. Extraction can be achieved in hot water. The extraction juices are then filtered, concentrated under vacuum and then dried by atomization. According to the present invention hydro-alcoholic extracts, tinctures containing 60 or 40% alcohol, fluid alcoholic (30%) or propylene-glycolic (40%) extracts can be used.
The dry sage extract is generally characterized by the presence of ursolic acid, flavonoids (lutenolin and apigenin glucosides), rosmarinic acid, picrosalvin as well as of various terpenic products such as tujone, borneol, salvene, pinene, bornyl acetate and linolyl acetate. The dry extract appears as a fine powder, having a color ranging from a yellowish brown to a brown. The dry extract is 1% soluble in water and slightly soluble in alcohol at 60° C. and barely soluble in alcohol at 95° C.
The soft passiflore or Passiflora incarnata extract is obtained by aqueous or hydro-alcoholic extraction of the above-ground sections of the plant, then through concentration to obtain a pasty mass having a solid content of greater than 60% and preferably about 80%. In terms of active principles, the extract which appears as a very dark brown paste contains vitexin, isovitexin, orientin and isoorientin. A 2% solution in 50% ethanol (by volume) is clear or slightly opalescent.
When the compositions of the present invention are intended for cosmetic applications, they preferably are prepared as an emulsion, a cream, a milk, a gel, a lotion, a poultice or an aerosol foam.
The compositions suitable for topical application have a thinning and anti-cellulite action especially when they are linked to other vegetable extracts and/or other active principles such as hydrosoluble organic compositions derived from mono methyl trisilanol such as mono methyl trisilanol manuronate which is sold by the EXYMOL Company as "Algisium" (aqueous solution containing 1% of mono methyl trisilanol manuronate) or the lactate which is sold by EXYMOL Company as "Lasilium" (aqueous solution which contains 1% of mono methyl trisilanol lactate). The latter compositions can be present in concentrations from 2 to 20% of 1% solutions or from 0.02 to 0.2% by weight expressed in active matter.
The compositions can contain other traditional ingredients such as perfumes, coloring agents, preservatives, thickeners and solvents.
According to a preferred embodiment of the present invention, the compositions are intended for pharmaceutical use in cases of venous or capillary insufficiency. The compositions especially are applied in phlebology and venous-related syndromes such as "heavy legs", leg ulcers, phlebitis, chilblains, in gynecology with respect to some dysmenorrheas, and in proctology for the treatment of simple hemorrhoids and hemorrhoidal anitis.
Pharmaceutical compositions which are intended for systemic application can be prepared, for instance, by adding extracts as defined above as active substances, to solid or liquid conventional non-toxic inert supports. These compositions can be administered enterally, parenterally or topically. With respect to enteral administration, the compositions are prepared in the form of pills, granules, capsules, lozenges, syrups, suspensions, solutions or suppositories. The dosage is obviously dependent on the method of administration and the desired activity.
For instance in proctology, suppositories might contain, per unit, in an excipient that is comprised of semi-synthetic glycerides:
0.01 to 0.05 g of dry sage extract,
0.01 to 0.03 g of dry fragon extract, and preferably:
0.01 to 0.03 g of soft passiflore extract.
Pharmaceutical compositions can contain inert additives or those which are possibly pharmaco-dynamically active. Pills or granules can contain binding agents, fillers, supports or diluents. Liquid compositions can be present for instance in the form of a sterile water miscible solution. In addition to extracts, capsules can contain a filler or thickening agent. Orally administered pharmaceutical compositions can also contain taste improving agents and substances which are generally used as preservatives, stabilizers, regulators and emulsifiers.
The supports and diluents mentioned above are comprised of organic or mineral substances, such as gelatin, lactose, starch, magnesium stearate, talcum, arabic gum or poly-alkylene-glycols. When pharmaceutical compositions are intended for topical applications, they are prepared in the form of ointments, pomades, tinctures, creams, solutions, lotions, sprays or suspensions. Ointments or pomades are preferred and they are prepared by mixing the extracts according to the invention as active consituents with inert non-toxic supports which are suitable for topical treatment.
For example, a cream used to treat heavy legs, periphlebitis, hypodermitis or chilblains, contains in an appropriate excipient for a 100 g sample,
0.3 to 3.5 h of dry sage extract, and
0.3 to 2.5 h of dry fragon extract, and preferably:
0.2 to 1.5 g of a soft passiflore extract.
Measuring Activity on Capillary Brittleness by the Petechia Method.
This method is commonly used to determine capillary brittleness and was described in the article by J. L. PARROT and P. CANU, "Factors which heighten the resistance of capillaries" Int. Pharmaco-dyn. Arch. No. 1, p. 152 (1964). The principle and method shall be explained below.
The principle involves inducing the appearance of petechiae on part of the back skin of rats with a vacuum chamber, which enables the measurement of capillary resistance where time=0. Then the composition to be tested is applied on an adjacent and defined skin zone which leads to a change in resistance of the capillary in that skin zone. The change in resistance is recorded on various parts of the skin which are treated at regular time intervals (30 min., 1 hr., 1 hr. 30 min., 2 hrs., 2 hrs. 30 min.). The experiment ends with a final measurement on part of the untreated skin to verify that the control measurement at time =0 did not change.
The apparatus enabling the measurement is derived from that which is described by R. CHARLIER, A. HOOSLET and M. COLOT, "Experimental investigations on vascular brittleness" Int. Arch. of "Physiology and Biochemistry", 71, (1), 1963. The apparatus includes a vacuum pump which is connected to a vacuum tank which is itself connected to a manometer that enables measurement of the vacuum expressed in mm of Hg. A flask is inserted between the vacuum tank and the manometer and acts as a buffer zone. A cell which is connected to a glass pipe controlled by a faucet enables the application of pressure onto the skin. The cell has a diameter of about 5 mm and it includes flat edges so as to prevent skin distortion.
For each composition to be tested, the measurements of capillary resistance were achieved on 16 WISTAR while male rats (weight 300-400 g) of which the lower dorsal section was shaved and depilated, and the animals were left resting for 48 hrs. prior to the experiment.
At the onset of experimentation, the capillary resistance threshold for each rat is measured by applying a vacuum of 300 mm of Hg for 15 seconds then by increasing such vacuum by 5 mm of Hg until petechiae appear (4 or 5 petechiae).
After this measurement is achieved, the composition to be tested is then applied (2 mg/cm 2 ) on an adjacent and defined section of skin and the vacuum required to produce petechiae in various sites is measured every 30 min. The experiment stops after the 6th measurement, or after 2 hrs. 30 min.
Then the capillary resistance of an untreated section is measured to verify, that the capillary resistance measured at time t=0 did not suffer any notable changes.
According to this method, capillary resistance was assessed with the following compositions:
______________________________________(1) Placebo = excipient with the following composition:Polyacrylic acid (Carbopol 941) 0.2 g99% Triethanolamine 0.6 gPropylene glycol 5.0 gMethyl parahydroxybenzoate 0.1 gPropyl parahydroxybenzoate 0.2 gStearic acid 2.0 gSelf-emulsifying glycerol stearate 4.0 gCetyl alcohol 1.0 gVaseline oil 20.0 gSterile mineral-free water q.s.p. 100.0 g(2) P cream = Excipient + 0.5% of soft passiflore extract(3) S cream = Excipient + 0.5% of dry sage extract(4) F cream = Excipient + 1% of dry fragon extract(5) FP cream = Excipient + 1% of dry fragon extract + 0.5% of soft passiflore extract(6) PS cream = Excipient + 0.5% of soft passiflore extract + 0.5% of dry sage extract(7) FS cream = Excipient + 1% of dry fragon extract + 0.5% of dry sage extract(8) FSP cream = Excipient + 1% dry fragon extract + 0.5% of dry sage extract + 0.5% of soft passiflore extract______________________________________
The results observed are depicted in Table A below. The values obtained (mm/Hg) correspond to an average of measurements recorded on 16 rats treated with each cream.
TABLE A__________________________________________________________________________ time 2 hr.(sample) 0 1/2 hr. 1 hr. 11/2 hr. (sample) 21/2 hr. >21/2 hr.__________________________________________________________________________Placebo 1* 373.8 371.1 373.8 374.3 373.5 374.6 373.5 2** -- -0.7 0 +0.4 -0.1 +0.2 -0.1CreamP 1 379.1 382.2 387.5 390.0 390.3 385.3 380.3 2 -- +0.8 +2.2 +2.9 +3.0 +1.8 +0.3CreamS 1 364.4 366.5 370.6 374.7 376.2 376.6 366.8 2 -- +0.6 +1.7 +2.8 +3.3 +3.3 +0.6CreamF 1 376.5 380.9 388.2 392.3 394.3 391.2 378.5 2 -- +1.1 +3.1 +4.2 +4.8 +3.9 +0.5CreamFP 1 367.8 375.0 388.7 394.4 403.7 405.3 374.4 2 -- +1.9 +5.7 +7.2 +9.8 +10.2 +1.8CreamPS 1 370.0 372.8 380.6 387.8 390.6 392.8 373.4 2 -- +0.8 +2.9 +4.8 +5.6 +6.2 +0.9CreamFS 1 378.1 399.8 417.2 432.3 442.8 454.1 381.9 2 -- +5.7 +10.3 +14.3 +17.1 +20.1 +1.0CreamFSP 1 390.9 397.8 424.4 455.0 480.9 481.9 403.4 2 -- +1.8 +8.5 +16.4 +23.0 +23.3 +3.2__________________________________________________________________________ *1 = Average of values in mm of Hg **2 = % of development in relation to the sample (t = 0).
ANALYSIS OF FINDINGS
(1) The Placebo has no effect on capillary resistance.
(2) The soft passiflore extract very slightly increases capillary resistance (maximum of about 3% obtained after 2 hrs then a fast drop).
(3) The dry sage extract displays a maximum that is similar to the passiflore extract but it remains constant after 2 hrs.
(4) The dry fragon extract exercises notable activity on capillary resistance (about 4.5% between 1 hr and 2 hrs after being applied).
(5) The combination of fragon extract and passiflore extract exercises activity on capillary resistance, the latter rising to about 10% after 2 hrs-2 hrs 30 min. following application.
(6) The combination of soft passiflore extract and dry sage extract also displays an effect on capillary resistance but it is less pronounced (only 6% after 2 hrs 30 min.).
(7) The combination of dry fragon extract and dry sage extract has a significant synergistic effect on capillary resistance in relation to the dry fragon extract on the one hand and the dry sage extract on the other hand (increase of capillary resistance of about 20%).
(8) The combination of dry fragon extract, dry sage extract and soft passiflore extract induces a very high increase in capillary resistance.
If, with the averages which are recorded for each cream, the method of multiple comparison for averages by NEWMAN and KEULS (variance analysis) is applied, the ranks which are provided below are obtained. For a given time, the averages which were recorded for each cream are ranked in increasing order.
The averages which are underlined by a continuous line are not especially different from one another, otherwise the difference is significant with a 5% margin of error.
______________________________________(1) Time 1 hrCream S PS P FP F FS FSPAverage 370.6 380.6 387.5 388.8 388.2 423.4 424.4(2) Time 1 hr 30Cream S PS P F FP FS FSPAverage 374.7 387.8 390.3 392.3 394.4 432.3 455.0(3) Time 2 hrsCream S P PS F FP FS FSPAverage 376.2 390.3 390.6 394.4 403.7 442.8 480.9(4) Time 2 hrs 30Cream S P F PS FP FS FSPAverage 376.6 385.3 391.2 392.8 405.3 454.1 481.9______________________________________
The result of these rankings is that cream FS according to the invention after 1 hr 30 min. is significantly lower than cream FSP but it is significantly higher than the other creams after 2 hrs. After 2 hrs 30 min., creams FS and FSP are not significantly different from one another but they are significantly greater than the other creams.
Now we will provide as an illustration without restriction of several examples of vegetable extract-based compositions according to the present invention:
______________________________________EXAMPLE 1: Thinning cream______________________________________Isopropyl palmitate 3.0Soy oil 6.0Triple pressure stearic acid 4.0Cetyl alcohol 4.0Glycerol monostearate 4.0Methyl parahydroxybenzoate 0.2Propyl parahydroxybenzoate 0.199% triethanolamine 0.8Vegetable extracts:Dry sage extract (aqueous extract) 2.0Dry fragon extract (water-saturated 2.0n-butanolic extract)Perfume 0.3Sterile deionized water Q.S.P. 100% by weight______________________________________
______________________________________EXAMPLE 2: Relaxing body milk for "heavy legs"______________________________________Vaseline oil 16.0Isopropyl palmitate 2.0Liquid lanolin 1.0Triple pressure stearic acid 2.5Glycerol stearate 2.599% triethanolamine 0.8Methyl parahydroxybenzoate 0.2Propyl parahydroxybenzoate 0.1Vegetable extracts:Dry fragon extract (water-saturated 0.5n-butano1ic extract)Dry sage extract (aqueous extract) 0.5Perfume 0.5Deionlzed water Q.S.P. 100% by weight______________________________________
______________________________________EXAMPLE 3: Relaxing gel for "heavy legs"______________________________________Polyacrylic acid (Carbopol 940) 1.099% triethanolamine 1.0Propylene glycol 8.0Methyl parahydroxybenzoate 0.1Propyl parahydroxybenzoate 0.2Perfume 0.3Vegetable extracts:Dry fragon extract (water-saturated 1.5n-butanolic extract)Sage extract (aqueous extract) 0.3Soft hydro-alcoholic passiflore extract 1.5Steri1e deionized water Q.S.P. 100% by weight______________________________________
______________________________________EXAMPLE 4: Cream for roseola______________________________________Triple pressure stearic acid 3.0Cetyl alcohol 3.0Glycerol stearate 3.0Sorbitan polyoxyethylene mono-oleate 3.0Sunflower oil 10.0Propylene glycol 4.0Sorbitol 4.0Methy1 parahydroxybenzoate 0.2Propyl parahydroxybenzoate 0.1Perfume 0.3Vegetable extracts:Dry fragon extract (water-saturated 0.3n-butanolic extract)Dry sage extract (aqueous extract) 0.1Soft hydroalcoholic passiflore 0.1extract (containing 76.5% of solidmatter)Sterile deionized water Q.S.P. 100% by weight______________________________________
______________________________________EXAMPLE 5: Ointment for varicose veins______________________________________lsopropyl myristate 90.5 gSilica (sold as AEROSIL 200 by the 8.0 gDEGUSSA Company)Vegetable extracts:Dry fragon extract (water-saturated 0.5 gn-butanolic extract)Dry sage extract (aqueous extract) 1.0 g______________________________________
______________________________________EXAMPLE 6: Suppositories for hemorrhoids(composition per unit)______________________________________Vegetable extracts:Dry fragon extract (water-saturated 0.02 gn-butanolic extract)Dry sage extract (aqueous extract) 0.02 gSoft hydro-alcoholic passiflore 0.02 gextract (containing 76.5% of solidmatter)Triglycerides of caprylic and capric 0.2 gacidsSemi-synthetic glycerides Q.S.P. 2.0 g______________________________________
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A composition for cosmetic or pharmaceutical use is disclosed. The composition contains a cosmetically or pharmaceutically acceptable carrier, and a combination of vegetable extracts comprising:
(i) a fragon extract (Ruscus aculeatus L.), and
(ii) a sage extract (Salvia officinalis L.).
The composition can be used for the treatment of capillary brittleness by reducing capillary permeability and by increasing capillary resistance.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention generally relates to the design of sliding sleeve valves. In particular aspects, the invention relates to systems and methods for securing a sliding sleeve valve in an open or closed position.
[0003] 2. Description of the Related Art
[0004] Sliding sleeve valves are used extensively in hydrocarbon production wellbores. A sliding sleeve valve generally includes an outer housing that defines a central flowbore. The housing has one or more lateral fluid flow ports defined therein. A sleeve member is disposed within the flowbore and is axially moveable with respect to the housing between a first position, wherein the one or more lateral fluid ports is blocked, and a second position, wherein the one or more fluid ports is open.
[0005] In situations wherein a sleeve valve is incorporated into a production tubing string or other work string, wireline tools are often passed down through the center of those strings to conduct operations below the sleeve valve. These tools may inadvertently shift the sleeve within the sleeve valve, which is not desirable.
SUMMARY OF THE INVENTION
[0006] The devices and methods of the present invention provide systems and methods for locking a sliding sleeve valve in an open position and/or a closed position to prevent inadvertent operation of the sleeve valve during other operations.
[0007] In a preferred embodiment, a sliding sleeve mechanism includes an outer sleeve housing which defines an axial flowbore. One or more lateral fluid communication ports are disposed through the sleeve housing to permit fluid communication between the flowbore and the annulus radially surrounding the housing. A sliding sleeve member is slidingly disposed within the flowbore of the sleeve housing an is moveable between a first position, wherein the lateral fluid communication ports are unblocked by the sleeve to permit fluid communication between the annulus and the axial flowbore, and a second position, wherein fluid communication between the annulus and the flowbore is not permitted through the ports.
[0008] In various embodiments, the sliding sleeve mechanism is operably associated with a locking device which is operable to secure the sleeve member in open and/or closed positions. The locking device includes a housing bore portion with one or more locking grooves. The locking device also includes a sliding sleeve collet which is affixed to or integrally formed with the sliding sleeve member. The sliding sleeve collet includes a plurality of collet fingers with radially outwardly extending tabs which are shaped and sized to reside within the locking grooves of the housing bore portion.
[0009] The locking device also includes a collet locking member which resides radially within the sliding sleeve collet. In one embodiment, the collet locking member is a sleeve which includes an annular body with one or more collet fingers extending therefrom. The collet fingers have radially outwardly projecting tabs which releasably reside within one of a number of channels formed within an interior radial surface of the sliding sleeve collet. In this embodiment, a dog member is retained within an opening in the sliding sleeve collet. Movement of the collet locking member relative to the sliding sleeve collet will urge the dog member radially outwardly and into one of the surrounding locking grooves, thereby securing the sliding sleeve collet in place within the surrounding housing. When the dog member is moved radially inwardly, it operably interconnects the sliding sleeve collet and the collet locking member together.
[0010] A further embodiment is described wherein the sliding sleeve collet includes collet fingers which project in opposite axial directions. The collet locking member is an annular sleeve which can be moved axially within the sliding sleeve collet to positions wherein the body of the collet locking member retains one or more of the collet fingers of the sliding sleeve collet within a selected locking groove within the housing bore portion.
[0011] The locking device can be operated using a shifting tool which can engage portions of the collet locking member and move it axially with respect to the surrounding housing. The shifting tool preferably includes an engagement profile that selectively engages the collet locking member. As the collet locking member is moved within the housing, it also moves the surrounding sliding sleeve collet and the affixed sliding sleeve member between open and closed positions. Movement of the collet locking member with respect to the sliding sleeve collet will lock and unlock the sliding sleeve collet.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The advantages and other aspects of the invention will be readily appreciated by those of skill in the art and better understood with further reference to the accompanying drawings in which like reference characters designate like or similar elements throughout the several figures of the drawings and wherein:
[0013] FIG. 1 is a side, partial cross-sectional view of a portion of a wellbore containing a hydrocarbon production string with a sliding sleeve assembly.
[0014] FIG. 2 is an enlarged, cross-sectional view of a locking bore portion of the sliding sleeve valve housing for an exemplary sliding sleeve assembly.
[0015] FIG. 3 is a side, cross-sectional view of an exemplary sliding sleeve locking assembly in accordance with the present invention, in an open-unlocked configuration.
[0016] FIG. 4 is a side, cross-sectional view of the sliding sleeve locking assembly shown in FIG. 3 , now in a closed-unlocked configuration.
[0017] FIG. 5 is a side, cross-sectional view of the sliding sleeve locking assembly shown in FIGS. 3 and 4 , now in a closed-locked configuration.
[0018] FIG. 6 is a side, external view of a sliding sleeve collet member apart from other components of the locking assembly.
[0019] FIG. 7 is a side, cross-sectional view of the sliding sleeve collet member shown in FIG. 6 .
[0020] FIG. 8 is a side, external view of an exemplary collet locking member apart from the other components of the locking assembly.
[0021] FIG. 9 is a side, cross-sectional view of the collet locking member shown in FIG. 8 .
[0022] FIG. 10 is a side, cross-sectional view of an exemplary shifting tool for use in operating the sliding sleeve assembly of FIGS. 2-9 .
[0023] FIG. 11 is an axial cross-section taken along lines 11 - 11 in FIG. 10 .
[0024] FIG. 12 is a side, cross-sectional view of an alternative sliding sleeve locking assembly, in an open-locked configuration.
[0025] FIG. 13 is a side, cross-sectional view of the locking assembly shown in FIG. 12 , now in an open-unlocked configuration.
[0026] FIG. 14 is a side, cross-sectional view of the locking assembly shown in FIGS. 12-13 , during shifting.
[0027] FIG. 15 is a side, cross-sectional view of the locking assembly shown in FIGS. 12-14 , now in a closed-unlocked configuration.
[0028] FIG. 16 is a side, cross-sectional view of the locking assembly shown in FIGS. 12-15 , now in a closed-locked configuration.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] As used in the discussion herein, the terms “up,” “down,” “upper,” “lower,” “above,” “below,” “upwardly,” “downwardly,” as well as other terms and their respective derivations, refer to relative, rather than absolute positions or orientations. Those of skill in the art will understand that various components and assemblies used within the described sliding sleeve locking assemblies may be reversed within a sliding sleeve valve and still provide desired function.
[0030] FIG. 1 illustrates a portion of an exemplary wellbore 10 that has been drilled through the earth 12 and which has been lined with casing 14 . A production tubing string 16 is shown disposed within the wellbore 10 . An annulus 18 is defined radially between the production tubing string 16 and the casing 14 . The production tubing string 16 may be formed of a number of production tubing sections, of a type known in the art, which are interconnected to one another in an end-to-end fashion. The sections may be interconnected using threaded connections or by connecting collars or in other ways known in the art. Alternatively, the production tubing string 16 may be formed of coiled tubing, of a type known in the art. A central axial flowbore 20 is defined along the interior of the production tubing string 16 .
[0031] A sliding sleeve valve 22 is incorporated into the production tubing string 16 in a manner known in the art. The sliding sleeve valve 22 is typically employed as a production nipple that can be selectively opened to permit production fluids within the wellbore 10 and from surrounding hydrocarbon-bearing formations to be flowed into the flowbore 20 of the production tubing string 16 and pumped to the surface of the wellbore 10 . If desired, the sliding sleeve valve 22 may be axially isolated from other portions of the wellbore 10 by packers (not shown) which are set within the annulus 18 of the wellbore 10 . The sliding sleeve valve 22 has a radially outer housing 24 with lateral fluid flow ports 26 disposed therethrough. The lateral ports 26 permit fluid communication between the annulus 18 and the interior of the housing 24 of the sleeve valve 22 so that fluid entering the valve 22 may be flowed to the surface of the wellbore 10 via the flowbore 20 . The sliding sleeve valve 22 also includes a sliding sleeve member 28 which is slidably disposed within the housing 24 and is, as is well known, moveable between a first, closed position, wherein the sleeve member 28 blocks the ports 26 against fluid flow, and a second, open position, wherein fluid flow is permitted through the ports 26 .
[0032] The sliding sleeve valve 22 incorporates a sliding sleeve valve locking assembly, generally indicated at 30 , which is capable of securing the valve 22 in its closed and/or its open position. In general, the locking assembly includes a locking bore portion in an outer housing having one or more locking grooves formed within.
[0033] The locking assembly also includes a sliding sleeve collet, which is secured to or integrally formed with the sliding sleeve member 28 , and a collet locking member which resides radially within the sliding sleeve collet. In preferred embodiments, the locking mechanism is actuated using a shifting tool 29 , which is visible in FIG. 1 being disposed within the flowbore 20 of the production tubing string 16 . The construction and operation of exemplary locking assemblies will be described in greater detail with respect to FIG. 2 et seq.
[0034] FIG. 2 depicts a locking bore portion 31 of the interior surface 32 of the sliding sleeve valve housing 24 apart from other components of the valve 22 . The interior surface 32 has an upper latching groove 34 and lower locking groove 36 inscribed therein. Upper and lower secondary latching grooves 38 , 39 , respectively, are also inscribed within the interior surface 32 .
[0035] FIG. 3 depicts an exemplary sliding sleeve locking assembly 40 which is located within the sliding sleeve valve housing 24 . The locking assembly 40 includes a sliding sleeve collet member 42 which resides within the locking bore portion 31 of the housing 24 . The sliding sleeve collet member 42 is depicted in greater detail in FIGS. 6 and 7 , wherein it is shown apart from the other components of the locking assembly 40 . The sliding sleeve collet member 42 has a generally cylindrical body 44 with a dog opening 46 disposed therethrough. Above the dog opening 46 are a plurality of vertically disposed slots 48 which are cut through the body 44 . In addition, a number of generally U-shaped slots 50 are formed in the body 44 to define downwardly extending collet fingers 52 . The lower end of each of the fingers 52 present radially outwardly extending tabs 54 . In addition, a smaller radially outwardly extending tab 56 extends about the periphery of the body 44 .
[0036] The interior radial surface 58 of the collet member 42 (shown in FIG. 7 ) has a radially inwardly extending flange 60 at the upper axial end 62 . Upper and lower annular channels 64 and 66 , respectively, are formed into the interior surface 58 below the flange 60 . A radially inwardly directed tab 68 extends from the lower end of each finger 52 .
[0037] The locking assembly 40 also includes an annular collet locking member 70 which resides radially within the sliding sleeve collet member 42 . FIGS. 8 and 9 depict the collet locking member 70 apart from the other components of the locking assembly 40 . The collet locking member 70 includes a generally cylindrical base ring 72 with a plurality of axially extending collet fingers 74 . The base ring 72 is corrugated so that the interior radial surface 76 of the base ring 72 presents an upwardly directed contact shoulder 78 . The exterior radial surface 80 of the base ring 72 defines an annular dog recess 82 which is bounded by chamfered shoulders 84 . A dog member 86 resides within the dog recess 82 and the dog opening 46 of the sliding sleeve collet member 42 . The upper ends of the collet fingers 74 each present a radially inwardly directed flange 88 which presents a downwardly axially-facing shoulder 90 . In addition, the collet fingers 74 each present a radially outwardly-projecting tab 92 , which is shaped and sized to reside within the annular channels 64 or 66 in a complimentary manner.
[0038] FIGS. 10 and 11 illustrate in greater detail the exemplary shifting tool 29 which can be used to actuate the locking assembly 40 . The shifting tool 29 presents a bullnose leading end 94 and a generally cylindrical body 96 with a plurality of axial slots 98 disposed through the body 96 in an angularly spaced relation about the body 96 to form a series of substantially parallel ribs 100 . Each rib 100 is provided with a radially outwardly extending engagement profile 102 which is shaped to present a first axially directed shifting shoulder 104 and a second shifting shoulder 106 , which is directed in the opposite axial direction from the first shoulder 104 .
[0039] In operation, the shifting tool 29 can be used to shift the sleeve member 28 between open and closed positions as well as actuate the locking assembly 40 between locked and unlocked configurations. When the locking assembly 40 is in a locked configuration, the sleeve member 28 is secured against inadvertent movement with respect to the surrounding housing 24 , thereby making it unlikely that the sliding sleeve valve 22 will be inadvertently operated. FIG. 3 depicts the sleeve valve 22 in an open position so that fluid may enter the flowbore 20 of the production tubing string 16 from the annulus 18 . Also, FIG. 3 shows the locking assembly 40 in an unlocked configuration. The tabs 54 of the sliding sleeve collet member 42 are located within the recess 38 . The tabs 56 are located within the recess 34 .
[0040] In order to move the sleeve valve 22 and the locking assembly 40 from the open-unlocked position shown in FIG. 3 to the closed-unlocked configuration shown in FIG. 4 , the shifting tool 29 is disposed into the flowbore 32 and moved downwardly until the shifting shoulder 106 of the shifting tool 29 engages the contact shoulder 78 of the collet locking member 70 , as depicted in phantom in FIG. 4 . Further movement of the shifting tool 29 in the direction of arrow 108 in FIG. 4 will move the collet locking member 70 axially in that direction. Movement of the collet locking member 70 in the direction of arrow 108 will also cause the sliding sleeve collet member 42 to be moved due to the presence of the dog member 86 , which operably interlocks the sliding sleeve collet member 42 with the collet locking member 70 . As the sliding sleeve collet member 42 is urged axially, the fingers 52 are deflected radially inwardly by sliding, ramping interaction between the outwardly extending tabs 54 and the angled side surfaces of the recess 38 . The tabs 56 are also deflected inwardly out of the groove 34 . As a result, the sliding sleeve collet member 42 is freed to move axially within the housing 24 until it reaches the closed-unlocked position shown in FIG. 4 .
[0041] When the sliding sleeve collet member 42 is moved to the position shown in FIG. 4 , the outwardly extending tabs 54 of the fingers 52 will snap into the latching groove 39 . It is noted that, in this position, the dog member 86 is located adjacent to the lower groove 36 . Further axial force upon the collet locking member 70 will cause the dog member 86 to be moved radially outwardly by sliding, ramping contact from chamfered shoulder 84 into the groove 36 . As shown in FIG. 5 , the radial outward movement of the dog member 86 will release the interconnection of the collet locking member 70 and the sliding sleeve collet member 42 . The collet locking member 70 can now be moved axially with respect to the sliding sleeve collet member 42 . The tabs 92 on collet fingers 74 will slide out of the upper annular channel 64 on the sliding sleeve collet member 42 and snap into the lower annular channel 66 . This will secure the collet locking member 70 in a position wherein the exterior radial surface 80 of the base ring 72 retains the dog member 86 within the groove 36 . This is the closed-locked position wherein the sliding sleeve valve 22 is secured in a closed position by the dog member 86 and the location of tabs 54 within the latching groove 39 . It can be seen that, when the tabs 92 of the collet locking member 70 are located in the upper channel 64 , this corresponds to an unlocked position wherein the dog member 86 can move radially inwardly to reside partially within the dog recess 82 in the collet locking member 70 and the sliding sleeve collet member 42 is unlocked and free to move with respect to the surrounding housing 24 . Conversely, when the tabs 92 of the collet locking member 70 are located in the lower channel 66 , this corresponds to a locked position wherein the dog member 86 is moved radially outwardly to partially reside within the groove 36 and the sliding sleeve collet member 42 is locked against movement with respect to the surrounding housing 24 .
[0042] In order to shift the sliding sleeve valve 22 back out of the closed-locked position, to an open position the shifting tool 29 is moved axially within the sliding sleeve valve housing 24 and is moved until the shifting shoulder 104 of the shifting profile 102 engages the shoulder 90 of the collet locking member 70 . The collet locking member 70 is pulled upwardly, and the tabs 92 of the collet locking member 70 are moved out of the lower channel 66 and back into the upper channel 64 of the sliding sleeve valve housing 24 (i.e., the position shown in FIG. 4 ). The dog member 86 is now freed to move radially inwardly and out of the locking groove 36 in the housing 24 . Further upward movement of the shifting tool 29 will move the collet locking member 70 and the operably connected sliding sleeve collet member 42 upwardly in the housing 24 . The locking assembly 40 will be returned to the open-unlocked position shown in FIG. 3 .
[0043] Those of skill in the art will recognize that the sleeve valve 22 may be constructed so that the open and closed positions of the sliding sleeve valve 22 may be reversed from what is described herein. In other words, the sleeve valve 22 may be in an open position when the locking assembly 40 is in the lower position shown in FIGS. 4 and 5 . Conversely, the sleeve valve 22 may be in a closed position when the locking assembly 40 is in the upper position shown in FIG. 3 .
[0044] FIGS. 12-16 illustrate an alternative sliding sleeve locking assembly 120 which is constructed in accordance with the present invention and associated with a sliding sleeve valve 22 , as described previously. The locking assembly 120 includes an outer housing 24 ′ which defines a locking bore portion 31 having an upper latching groove 34 ′ and lower latching groove 36 ′ (visible in FIGS. 15 and 16 ). In this embodiment, grooves 38 ′ and 39 ′ are smaller grooves than latching grooves 34 ′, 36 ′. The sliding sleeve collet member 42 ′ is, like the sliding sleeve collet 42 , operably affixed to the sleeve member 28 of the sliding sleeve valve 22 . The sliding sleeve collet member 42 ′ is provided with bi-directional collet fingers 52 a and 52 b . Collet fingers 52 a extend upwardly toward the upper axial end 62 of the sliding sleeve collet member 42 ′. The collet fingers 52 b extend downwardly away from the upper axial end 62 . Tabs 54 extend radially outwardly from the distal end of each collet finger 52 a , 52 b , and inwardly-directed tabs 68 extend radially inwardly from the distal end of the collet fingers 52 a , 52 b . Minor tabs 56 also protrude radially outwardly from each of the collet fingers 52 a , 52 b.
[0045] The collet locking member 70 ′ is generally cylindrically-shaped and resides radially within the sliding sleeve collet member 42 ′. The collet locking member 70 ′ presents an exterior radial surface 122 . Preferably, the exterior radial surface 122 presents upper and lower radially outward projections 124 , 126 . In addition, the collet locking member 70 ′ has an interior radial surface 128 which presents an upwardly-facing engagement shoulder 130 and a downwardly-facing engagement shoulder 132 .
[0046] In operation, the locking arrangement 120 can be moved by shifting tool 29 between an open-locked configuration, which is shown in FIG. 12 and a closed-locked configuration, which is depicted in FIG. 16 . In FIG. 12 , the sleeve member 28 is located within the surrounding housing 24 ′ at a location which corresponds to an open condition for the sleeve valve 22 . The affixed sliding sleeve collet member 42 ′ is locked into position within the locking bore portion 31 of the housing 24 ′ by the location of tabs 54 within latching groove 34 ′. The collet locking member 70 ′ is located within the sliding sleeve collet member 42 ′ such that the exterior radial surface 122 is in contact with the inwardly-protruding tabs 68 of each of the upwardly-extending collet fingers 52 a . As a result, the outwardly projecting tabs 54 are locked within the groove 34 ′. In addition, the tabs 56 of each of the collet fingers 52 a reside within the groove 38 ′. FIG. 13 shows that the shifting tool 29 has been moved into the locking arrangement 120 until the engagement shoulder 106 of the shifting tool 29 engages the engagement shoulder 130 of the collet locking member 70 ′. In FIG. 13 , the shifting tool 29 has moved the collet locking member 70 ′ downwardly, in the direction of arrow 134 , so that the sliding sleeve collet member 42 ′ is no longer locked into the groove 34 ′.
[0047] FIG. 14 shows the locking arrangement 120 at a further point during shifting wherein the projection 126 contacts the tab 68 of the sliding sleeve collet member 42 ′ so that downward movement of the collet locking member 70 ′ will also move the surrounding sliding sleeve collet member 42 ′ downwardly.
[0048] In FIG. 15 , the locking arrangement 120 has been shifted to a configuration wherein the sleeve member 28 now closes off fluid flow through the valve 22 . In this configuration, the outwardly-projecting tabs 54 of each of the collet fingers 52 b have become aligned with and snap outwardly into the lower latching groove 36 ′ to locate the sliding sleeve collet member 42 ′ at the proper location within the housing 24 ′. When this occurs, further downward movement of the sliding sleeve collet member 42 ′ with respect to the surrounding housing 24 ′ is stopped. As the shifting tool 29 is moved further downwardly, the collet locking member 70 ′ will be moved to the position shown in FIG. 16 wherein the outer radial surface 122 contacts the tabs 68 to retain the outwardly extending tabs 54 within the groove 36 ′. The shifting tool 29 may now be withdrawn from the locking assembly 120 by moving it upwardly.
[0049] It should be understood that the locking arrangement 120 is capable of selectively securing the sliding sleeve valve 22 in an open position (i.e., the open-locked position of FIG. 12 ) as well as the closed position (i.e., the closed-locked position of FIG. 16 ).
[0050] Those of skill in the art will recognize that numerous modifications and changes may be made to the exemplary designs and embodiments described herein and that the invention is limited only by the claims that follow and any equivalents thereof.
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Systems and methods for locking a sliding sleeve valve in an open position and/or a closed position to prevent inadvertent operation of the sleeve valve during other operations.
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This is a continuation of application Ser. No. 484,224 filed June 28, 1974 now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to impact devices and more specifically to pneumatic impact devices.
The invention can be used to the best advantage for making holes in compacted soils, and for driving pipes, earthing electrodes and wooden or metal sheet piles into the ground.
Known in the Prior Art art are pneumatic impact devices used, for example, for making holes in the ground, consisting of a casing, a ram and an air-distributing mechanism. However, these devices are not in widespread use due to their inherent disadvantages.
It happens frequently that the device which has stopped in the hole cannot be restarted and must be removed which is not always possible. These disadvantages are attributable mostly to an imperfect design of the air-distributing mechanisms which are highly sensitive to impact load, deformations of the casing and jamming of the ram in the casing.
The above disadvantages can be eliminated to a considerable extent with the aid of devices in which the air-distributing mechanisms are installed on a damper.
OBJECTS AND SUMMARY OF THE INVENTION
Such devices include pneumatic impact devices comprising a hollow cylindrical casing accommodating a ram, a stepped slide valve, a flange, a tubular damper and a nut (see, for example, U.S. Pat. No. 3,410,354, Federal Republic of Germany Pat. No. 1,634,579. In these devices, the ram provided with an axial channel and radial channels in the tail part rests on the inner walls of the casing by two projections (with a provision of reciprocating motion) and its front end defines, together with the casing walls, a chamber which is filled with compressed air from a compressed air line through said channels and such air reciprocates the ram. The slide valve is a two-step bushing located in the tail part of the casing and its maximum-diameter step is located in the axial channel of the ram. The bushing communicates the source of compressed air with the radial channels which are periodically closed by said slide valve during the movement of the ram.
The minimum-diameter step of the bushing is connected by a tubular damper with a flange which is fastened rigidly to the tail part of the casing by a nut and has holes for the discharge of the used air.
Such a design of the air-distributing mechanism is highly involved. Besides, the ram often becomes jammed in the slide valve while the tubular damper is unreliable and short-lived which frequently leads to failures of the slide valve.
OBJECTS AND SUMMARY OF THE INVENTION
An object of the present invention resides in eliminating the aforesaid disadvantages.
An object of the invention consists in providing a pneumatic impact device which is compact and simple in design.
Another object of the invention consists in providing a device which is reliable in operation.
An important object of the invention consists in providing a device with a reliable system of air distribution without a slide-valve air-distributing mechanism.
Still another object of the invention consists in raising the impact power and output of the device and in reducing the consumption of compressed air.
These and other objects are achieved by providing a pneumatic impact device which comprises a hollow cylindrical casing, a nut which closes the open end of the casing, and a stepped ram provided with an axial channel and radial channels, said ram being located in the casing with a provision for reciprocating therein and defining by its front part, together with the casing walls, a chamber which is filled with compressed air from a compressed air line through said channels, said compressed air moving the ram for delivering an impact and then escaping outside through discharge holes in which, according to the invention, each succeeding step of the ram in the direction from the nut to the front end of the ram has a larger diameter than the preceding step, with the minimum-diameter step being located in the nut while the maximum-diameter step has longitudinal channels which open at one end into the chamber for placing it periodically in communication with the compressed air line.
Such a design ensures compactness, simplicity and reliability because this device has no slide-valve air-distributing mechanism. The provision of a three-step ram with longitudinal channels therein ensures efficiency of the device, reliable starting and simplicity of maintenance in operation.
To simplify the design of the device and reduce its size, it is practicable that the casing be provided with a circular recess which defines, together with the cylindrical surface of the maximum-diameter ram step, a space which communicates with the other ends of all the longitudinal channels.
The simplicity of design is achieved by making the ram with two steps which is possible due to the provision of a circular recess in the casing, communicating with the chamber through longitudinal channels.
It is also practicable that the other end of each longitudinal channel of the maximum-diameter step of the ram opens on the face surface of said step and that the cross-sectional area of these channels be smaller than that of the radial channels of the ram.
This ensures the discharge of the used air through the nut thereby dispensing with the side holes in the casing and improving the strength of the casing. For addition, in this case there is no need in the housing which is installed on the casing in order to protect the inside spaces of the device against dirt or foreign matter.
The cross-sectional area of the longitudinal channels must be two to five times smaller than that of the radial channels for ensuring the reversal of the ram.
To reduce the consumption of compressed air, it is practicable that the casing be provided with a circular recess which defines, together with the cylindrical surface of the minimum-diameter ram step, a space which is in constant communication with the atmosphere through the longitudinal holes in the nut, with said holes also serving as discharge holes while each longitudinal channel communicates with the space at the end of the back stroke of the ram.
The reduction of air consumption is achieved because the longitudinal channels place the chamber in communication with the atmosphere via the space not constantly but only at the end of the back stroke of the ram.
In the designs described above, the pressure of the compressed air acts not on the maximum cross-sectional area of the ram but on its minimum-diameter step which impairs the efficiency of the device.
To counter this disadvantage, it is necessary that the minimum-diameter step of the ram be provided with a projection and a bushing for joint movement with the ram, with said bushing having side holes and an external circular recess through which said space communicates periodically with the atmosphere through the longitudinal holes in the nut, that said holes open at one end on the internal cylindrical surface of the nut, with the latter being provided with inlet channels for the delivery of compressed air through the side holes of the bushing into said space when the ram moves towards the nut, and that the inlet channels of the nut open on its inner cylindrical surface.
Such a design increases the efficiency of the device since, in the course of the working stroke of the ram, the space is communicated with the source of compressed air which allows the maximum cross-sectional area of the ram to be used for its acceleration.
To make the invention more apparent, it will now be described in detail by way of example with reference to the accompanying drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of the pneumatic impact device according to the invention, the view being in longitudinal section; and
FIGS. 2 through 5 are side views of the versions of the device according to the invention, the views being longitudinal section.
DETAILED DESCRIPTION OF THE INVENTION
The pneumatic impact device for making holes in the ground according to the invention comprises a hollow cylindrical casing 1 (FIG. 1) which accommodates a stepped ram 2 and a nut 3 which closes the open end of the casing 1 and to which a compressed air line 4 is connected. The compressed air line is connected to a source of compressed air of any known type, e.g. a compressor.
The side walls of the casing 1 are provided with holes 5. The ram 2 has three cylindrical steps 6,7,8 whose diameters increase towards its front end. The front part of the maximum-diameter step 8 of the ram 2 defines, together with the walls of the casing 1, a working chamber 9. The cylindrical part of the ram step 7 and the side walls of the casing 1 define a space 10. The step 8 of the ram 2 has longitudinal channels 11 which communicate the working chamber 9 with the space 10. The ram 2 has radial channels 12 which open on the cylindrical surface of the step 7 and communicate with an axial channel 13 which is in communication with the compressed air line. The inner cylindrical surface of the nut is made in the form of two steps 14 and 15 and has channels 16 which are open to the atmosphere at one end and communicate at the other end with a space 17 which is defined by the outer cylindrical surface of the step 6 of the ram 2 and by the inner cylindrical surface of the step 15 of the nut 3. The cylindrical surfaces of the ram steps 6 and 7 interact with the cylindrical surfaces, respectively, of the steps 14 and 15 of the nut 3. The compressed air line 4 is in constant communication with a space 18 which is defined by the face surface of the ram step 6 and by the cylindrical and face surface of the nut step 14. The front part of the casing 1 is provided with a protective housing 19 which keeps foreign matter from entering into the device.
To reduce the size of the device and to simplify its design, the casing 1 has a circular recess 20 (FIG. 2). The ram 2 is made in the form of two cylindrical steps 21 and 22. The cylindrical surface of the maximum-diameter step 21 of the ram 2 and the circular recess 20 of the casing 1 define a space 23 which communicates with the working chamber 9 through the longitudinal channels 11 of the ram 2.
The radial channels 12 of the ram 2 opening on the cylindrical surface of its step 21 communicate with the space 23 when the ram is in the front (working) position.
The nut 3 has an inner cylindrical surface 24 which interacts with the outer cylindrical surface of the minimum-diameter step 22 of the ram 2 and provides together with its face surface, a chamber 25. A space 26 is defined by the outer cylindrical surface of the ram step 22 and the inner walls of the casing 1 and is open to the atmosphere through the channels 16 of the nut 3.
To simplify the design of the device and increase the strength of the casing, the longitudinal channels 11 (FIG. 3) of the maximum-diameter step 21 of the ram 2 open on the face surface of such step and communicate the working chamber 9 with the atmosphere through the space 26 and the channels 16 of the nut 3. The cross-sectional area of the channels 11 of the ram 2 is considerably smaller (by two to five times) than that of the radial channels 12 of the ram 2. The inner recess 20 of the casing 1 has a shoulder 27. When the ram 2 in the forward position, its radial channels 12 communicate directly with the chamber 9.
To reduce the consumption of air, the casing 1 has an additional circular recess 28 (FIG. 4) with a shoulder 29. The recess 28 provides, together with the outer cylindrical surface of the minimum-diameter step 22 of the ram 2, a space 30 which is in constant communication with the atmosphere through the channels 16 of the nut 3. The longitudinal channels 11 of the ram 2 open at one end into the working chamber 9 while their other ends open on the outer cylindrical surface of the maximum-diameter step 21 of the ram 2. As the ram 2 moves towards the nut 3 and passes the shoulder 29 at the end of its the back stroke, the channels 11 place the chamber 9 in communication with the atmosphere through the space 30 and the channels 16 of the nut 3.
To increase the impact power and output of the device, the minimum-diameter step 22 of the ram 2 is provided with an outwardly extending projection or flange 31 (FIG. 5) and a bushing 32 which has side holes 33 and an outer circular recess 34 through which the space 30 is placed periodically in communication with the atmosphere through the channels 16 of the nut 3. One end of each channel 16 opens on the inner cylindrical surface 24 of the nut 3. The nut 3 has inlet channels 35 for the supply of compressed air from the air line 4 through side holes 33 into the space 30 when the ram 2 moves towards the nut 3.
Each channel 35 opens on the inner surface 24 of the nut 3. The inner surface of the bushing 32 has a recess 36 with an internal projection 37 which interacts with the projection 31 on the back stroke of the ram.
The device operates as follows:
In FIG. 1, as compressed air is delivered from the compressed air line 4 into the space 18, the air starts to flow through the channels 13 and 12 of the ram 2 into the space 10 and further, through the longitudinal channels 11, into the working chamber 9. Due to the difference between the areas of the face surfaces of the steps 8 and 6 of the ram 2, the ram starts moving towards the nut 3. During this movement, the radial channels 12 are covered by the inner cylindrical surface of the step 15 of the nut 3 so that the further movement of the ram 2 will be executed due to the expansion of the compressed air in the working chamber 9. At the end of the back stroke of the ram 2, the holes 5 of the casing 1 are placed in communication with the working chamber 9 and the compressed air is discharged from the working chamber 9 into the atmosphere. The ram is stopped during the back stroke and moved forward by the pressure of compressed air in the space 18. In the extreme forward position (at the end of the working stroke), the ram 2 imparts a blow to the casing 1, driving it into the ground. The radial channels 12 of the ram 2 communicate with the space 10, the compressed air is admitted into the working chamber 9 and the working cycle is repeated over again.
To prevent formation of an air bumper in the space 17 during the back stroke of the ram 2, the channels 16 of the nut 3 keep this space in constant communication with the atmosphere.
If the device is made as shown in FIG. 2, it functions similarly for except the fact that the compressed air enters the working chamber 9 through the space 23 and the channels 11. On the back stroke of the ram 2, its radial channels 12 are covered by the inner cylindrical surface of the casing 1.
When the device is constructed as shown in FIG. 3, it functions as follows.
As the compressed air is delivered from the air line 4 into the chamber 25, the air starts flowing through the channels 13 and 12 into the working chamber 9.
Due to the difference between the areas of the face surfaces of the steps 21 and 22 of the ram 2, the ram starts moving towards the nut 3. During this movement, the radial channels 12 are covered by the inner cylindrical surface of the casing 1.
The area through the longitudinal channels 11 is deliberately made smaller than that through the radial channels 12, and hence the working chamber 9 is filled with air when the ram 2 is in the front position and the radial channels 12 are open, so that the entire volume of the chamber 9 becomes suddenly filled whereas the discharge of air into the atmosphere is by a gradual flow through the channels 11 of the ram 2, through the space 26 and the channels 16 of the nut 3 within the entire back stroke of the ram 2. The gradual discharge (throttling) of the air during the back stroke of the ram 2 reduces the dynamic loads of the air discharge. The ram 2 is stopped at the end of the back stroke and is moved forward by the pressure of compressed air in the chamber 25. When the ram 2 is in the extreme forward position (at the end of the working stroke), it imparts blows to the casing 1, thus driving it into the ground. The radial channels 12 of the ram 2 communicate with the working chamber 9 which starts to be filled with compressed air and the working cycle is repeated again.
If the device is of the type shown in FIG. 4, it functions similarly to the device illustrated in FIG. 3 except for the fact that the air is discharged from the working chamber 9 not in the course of the entire back stroke of the ram but at the moment when the channels 11 have passed the shoulder 29 and are connected with the space 30.
If the device is in compliance with the construction illustrated FIG. 5, it functions as follows: when compressed air is supplied from the air line 4 into the chamber 25, it flows through the channels 13 and 12 of the ram 2 into the working chamber 9. Due to the difference between the areas of the face surfaces of the ram steps 21 and 22, the ram 2 starts moving towards the nut 3. During this movement, the radial channels 12 are covered by the inner cylindrical surface of the casing 1 so that the working chamber 9 is separated from the air line 4 and the back stroke continues to be executed due to the expansion of air in the chamber 9. At a preset distance from the beginning of the back stroke of the ram, the channels 11 pass beyond the shoulder 29 of the recess 28 of the casing 1 and the air is discharged from the chamber 9 into the atmosphere through the space 30, recess 34 of the bushing 32 and through the channels 16 of the nut 3. During the back stroke of the ram 2, its projection 31 comes to bear against the projection 37 of the bushing 32, and shifts it towards the nut 3 until the holes 33 of the bushing 32 are aligned with the channels 35 of the nut 3 which admits compressed air from the chamber 25 into the space 30. Under the pressure of the compressed air from the side of the chamber 25 and space 30, the ram begins moving on its working stroke. Upon covering a preset distance, the ram 2 comes to bear with its projection 31 against the front (in the drawing) edge of the recess 36 of the bushing 32 and continues moving together therewith. During the movement of the bushing 32, its holes 33 are covered by the inner cylindrical surface 24 of the nut 3 while the inlet channels 35 of the nut 3 are covered by the outer cylindrical surface of the bushing 32 thereby cutting off the space 30 from the chamber 25 and, as a consequence, from the compressed air line 4. During the remaining part of the working stroke, the ram 2 moves due to the expansion of air in the space 30 and to the pressure of air entering the channel 13 from the chamber 25. At the end of the ram working stroke, the circular recess 34 of the bushing 32 places the space 30 in communication with the atmosphere through the channels 16 of the nut 3 so that air is discharged from the space 30. Upon coming to the extreme front position, the ram 2 imparts blows to the casing 1 thus driving it into the ground. At this moment, the radial channels 12 of the ram 2 pass the projection 27 of the circular recess 20 of the casing 1 and connect the working chamber 9 with the compressed air line 4 via the channel 13 and the chamber 25. Compressed air is admitted into the chamber 9 and the working cycle is repeated again.
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The present invention relates to pneumatic impact devices and can be used to the best advantage for making holes in compacted soils.
The device is provided with a hollow casing which accommodates a stepped ram with the maximum-diameter step in its front part. This step has longitudinal channels which open at one end into a working chamber defined by the maximum-diameter step and the side walls of the casing and serving for receiving compressed air from the compressed air line, with the air moving the striker to impart a blow after which it is discharged through holes in the casing.
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BACKGROUND OF THE INVENTION
The present invention relates to a method and an apparatus for displaying an image and data obtained from a broadcast or other medium, and more particularly, to an image and data display method and apparatus for displaying data classified or individualized for each user synchronized with the image.
Further, the present invention relates to a method of providing information (hereinafter referred to as contents) on a network together with information of goods, including advertisements, and more particularly, to a method of providing the information of goods classified or individualized for each user in relation to the contents.
Recently services of broadcasting data such as characters and pictures, other than images, have been developed to broadcast character data using air waves and data delivery services such as satellite or a CATV. In future, when broadcasting becomes digital, a large amount of data can be transmitted simultaneously with the transmission of images using data compression techniques and the data multiplexing techniques and accordingly it is believed that these data broadcasting services will increase extensively.
The displaying methods used in the conventional data broadcasting will now be described below.
Regarding character broadcasting, data is multiplexed in an unoccupied area of the surface waves and air being transmitted and electric waves received by a receiving terminal are then divided into images and data. Since the data broadcast is not related to the images broadcast, the data is displayed separately from the display images. For example, as shown in FIG. 8 , a display screen is divided into two portions so that an image is displayed in one of the portions and data is displayed in the other. Generally, that images and data are displayed in a display screen alternately by a remote control operation. Another display method waits until reception of the data is completed before displaying it while an image is viewed. Since a temporary memory area is also provided in the terminal, it is used to receive and store the data for later viewing.
In any event, since the data is independent from the image, the data can be viewed at any time regardless of the image starting from the time of completing the reception of the data.
Further, in the service known as interactive television, data related to an image is transmitted together with the image. The data is multiplexed in the unoccupied area of the terrestrial and air waves to be transmitted in the same manner as the character broadcasting. When data related to a scene being viewed arrives at the terminal, a specific icon is displayed at a corner of the image to notify a viewer of the arrival. When the viewer designates display of the data, the display screen is divided into two portions as shown in FIG. 8 and the image and the data is displayed at the same time. There is also a method that displays an image and data on one display screen alternately.
However, recently, Internet television capable of viewing a home page (discussed below) on the Internet has been developed. The display method thereof is substantially identical with the character broadcasting and the home page is displayed without quite synchronizing with an image. Generally, the display method thereof involves the method of displaying a television image and the home page on two display screens at the same time as shown in FIG. 8 . Also, a method of displaying the television image and the home page on one display screen alternately is used. Further, in recent television programs, an address of a home page is often displayed to the viewers, requiring that the user input the address in order to view the home page by means of the Internet television.
The prior art pertinent to the interactive television and the Internet television is described in “The Age of Digital Televisions Has Come !”, Nikkei Trendy, '96, Oct., pp. 54-73 issued by Nikkei Home Co. in detail.
Next, there is the World Wide Web (WWW) on the Internet for providing contents on a network. In the WWW, contents provided therein are named in the home page. The home page is generally described by the script language known as HTML (Hyper Text Markup Language). Further, in HTML, the relationship among the home pages is defined as a hyper link. The user designates a WWW server and a home page by a unified format named the URL (Uniform Resource Locator). When the WWW server receives a request from the user, the WWW server transmits a proper home page to the user.
In a general method of providing information on goods in the WWW, advertisements (information of goods) relating to the home page are displayed in the same home page. Since the information of goods relative to the home page required by the user is provided, the power of appealing to the user so that the user buys goods is increased. Generally, the home page and the advertisement often correspond to each other in advance.
An information service considered by the present invention is described below using a definite example.
Recently, with improvement of the performance of hardware and the diffusion of network, the interactive information service can be easily realized. The interactive information service mentioned here is the information service having bidirectional characteristics in which not only can an information provider send information to the user one-sidedly but also the user can access the information provider positively. For example, the conventional television broadcasting and the radio broadcasting are one-way media from a television program provider to viewers and listeners, while the facsimile and telephone which are bidirectional media are used to realize the interactive information service such as a viewer participating in a program. Further, an experimental television program employing the Internet and the communication using other communication methods instead of the facsimile and telephone has also started. Henceforth, it is believed that information services using television broadcasting and the Internet together will increased with the boom of the Internet.
In such a bidirectional information service, an effective and efficient inquiry from the information provider to the users is important. Unless an inquiry is first made by the information provider, interaction is also not started. Considering the merits of the information provider, it is desirable that large effects are attained by the inquiry with reduced labor.
Considering how to provide information effectively, information (which is sometimes referred to as data since the information is contrasted with images) is sent together with images and accordingly it is desirable that both of the information and the images have relationship. Utilization methods include, for example, in a television program a questionnaire on the program is sent simultaneously or more detailed information of goods is sent in a television commercial. When a television terminal capable of accessing to the Internet or a CD-ROM is considered, an automatic access program to an address of a home page or data in the CD-ROM may be merely sent. In this manner, when the access method from the image to the information is defined, there is a merit that the viewers are attracted by the image and move to the bidirectional media immediately. At the same time, the viewers can know detailed information pertinent to the image easily.
As a method of providing information effectively, there is considered important that information suitable for each individual user is sent directly. For example, in a current television commercial and television shopping, the same image information is provided to all of the users uniformly. However, when it is realized that information of goods having appeal in fact can be provided to each individual user together with images on the basis of customer information (character and taste of users), the efficiency of marketing is improved remarkably. The customer information includes characters and taste of the users. At the same time, since information suitable to the user's Interest is sent to the user, the efficiency of reference to the information is also increased. Such individualization technique is called mass customization or one-to-one marketing. Further, when different information is sent to each user, the information provider's load is increased and a load of the network is also heavy. Accordingly, the users are classified by common characteristics so that information is provided to each classified user. The concept “classification” is also contained in the mass customization.
Problems in case where the above-mentioned interactive information service is applied to the conventional image and data display method are now described.
First, in character broadcasting, relationships are not specifically defined between images and data. Similarly, it is not premised that relationships exists between television images and home pages on Internet television. Accordingly, there was no problem even if the images and data were displayed in different display screens independently. Further, in the character broadcasting, even if the method of displaying data on the image was performed, it was sufficient only by notifying that preparation of display was completed after reception of data had been finished. However, in the information service pertinent to the present invention, since data relative to the images is treated, it is necessary to notify the users which scene of the images the data corresponds to.
However, data relative to images is displayed together with the images in the current interactive television. Accordingly, the display method in which a scene of the images to which the relative data corresponds is transmitted to the user. However, since it is not a display method in which the mass customization is premised and the same data is delivered to the users, data to be viewed synchronized with the images is all the same for the users.
SUMMARY OF THE INVENTION
It is an object of the present invention to solve the above problems in order to realize the above information service by providing an image and data display method in which the users are first notified that data classified or individualized for each user exists synchronized with images and the data is displayed synchronized with the images.
Further, in order to cause the users to access to relative data, existence of the relative data must be understood more easily. Since it is considered that a plurality of data are also sometimes related to a specific image scene, measures for identifying differences among the plurality of data easily are required. Accordingly, it is another object of the present invention to provide an image and data display method of notifying users which data is related to the image plainly.
In addition, since the images are media that change with time, the users have a desire to view the image continuously without disturbing the image by any obstacle. Accordingly, it is another object of the present invention to provide an image and data display method which ensures that relative data is provided to users without losing the continuity of images.
Furthermore, since the interactive information service described above aims at typical families, it is necessary that the users' terminals can be operated simply and used easily. Accordingly, it is another object of the present invention to provide an image and data display method which is simple to operate and easy to use.
Further, in order to spread the interactive information service widely into typical families, it is indispensable that the users' terminals be inexpensive. Accordingly, it is another object of the present invention to provide an image and data display method which can use inexpensive terminals.
Further, in the interactive information service, it is important that an information provider's intention is satisfied sufficiently so that information is given to the user of the target exactly. Accordingly, it is another object of the present invention to provide an image and data display method which can reflect the information provider's intentions.
Next, in the service of providing information of goods in the WWW, generally, the home page and the advertisement are often provided to the user in a one-to-one correspondence manner. Accordingly, the service of providing a classified or individualized advertisement to each user cannot be realized as it is.
It is another object of the present invention to provide and display information on goods classified or individualized for each individual user in relation to contents while the user refers to the contents. Particularly, in the case where information of a plurality of goods is selected and provided to a target user at the same time, the present invention relates to a method of solving any conflict that results.
According to the present invention, a method of displaying an image and data relative to a specific scene of the image, comprises (a) the step of selecting, when one of a plurality of images is selected, at least one data relative to the image simultaneously, (b) the step of determining a display condition including display and non-display of the relative data on the basis of a previously determined user identifier and utilization condition, (c) the step of determining, when a plurality of relative data are determined to be able to be displayed in the step (b), display priorities among the relative data, (d) the step of displaying a picture and character string indicative of contents of each relative data on the basis of the display priorities determined in the step (c) together with the image during display of the specific scene, (e) the step of displaying, when a picture and character string is selected, relative data corresponding to the selected picture and character string on the basis of the display condition, and (f) the step of displaying, when a command for displaying a list is inputted, a list of pictures and character strings displayed until now and, when at least one in the list is selected, displaying relative data corresponding to the selected picture and character string on the basis of the display condition.
In steps (a) and (b), the data relative to the image being displayed and customized for the user is selected. Further, in step (d), the user can be notified by the picture and the character string indicative of contents of the relative data that the relative data exists in the image scene. In addition, in the step (e), the relative data can be displayed synchronized with the image in response to the user's request.
Moreover, in the step (b), the display condition of the picture and the character string is determined on the basis of the utilization condition such as a size of the display terminal of the user. Similarly, in the step (e), when a plurality of relative data exist in the same image scene, the display priority such as the order of displaying the relative data is determined. In step (d), since the picture and the character string are displayed on the basis of the display priority and the display condition, the existence of the relative data can be transmitted to the user plainly.
Further, in the step (f), when the user inputs a command to display a list, a list of pictures and character strings displayed to the present is displayed. The user can select any one in the list and refer to the relative data. That is, the user can first view only the images continuously and refer to the relative data slowly later. Since there is provided a mode that the picture and the character string cannot be displayed, the mode can cope with the need of the user who wants to view only the picture on the whole image.
Furthermore, in the present invention, in the step (e), the whole display screen for displaying the relative data is divided into at least one image display area and at least one data display area. There is provided a mode for simultaneously displaying the image and the data relative to the image and a mode for displaying at least one piece of relative data on the whole display screen. When a command for changing over the display is input, the display mode is changed among the image display mode, the image and data simultaneous display mode and the data display mode. The user can select the mode in accordance with the user's purpose. In addition, since the operation of selecting the mode can be made by the button of the remote controller, there can be provide the function that the operation is simple and easy.
Further, in the present invention, in step (f), the number of relative data displayed in the list is limited and selection of relative data is made in accordance with the display priority when the limitation is exceeded.
Accordingly, the memory area can be kept small and consequently the cost of the terminal can be reduced.
Moreover, in the present invention, there is provided a mode in which the information provider can forcedly display the picture and the character string indicative of contents of the relative data. Even if the user sets the picture and the character string of the relative data not to be displayed, the picture and the character string are necessarily displayed for the relative data in the forced display mode and accordingly the intentions of the information provider can be satisfied sufficiently such that information can be transmitted to the user of the target exactly.
In the information-of-goods providing method according to the present invention, when the user selects contents, information of goods relative to the contents is also selected at the same time and whether the information of goods is displayed or not is determined for each user on the basis of the display condition of the information of goods. When a plurality of information items of goods can be displayed by the above process, the display priorities are determined among the information items of goods. Further, during display of the contents, data indicative of the contents of the information of goods is displayed together with the contents on the basis of the display priorities determined by the above processing. In addition, there is provided a memory area for temporarily storing all information of goods selected for each user and including the information of goods which cannot be displayed during reference of the contents by the user since the display priority thereof is low and the temporarily stored information of goods can be displayed in accordance with the user's request.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram illustrating a functional block of an image and data display method and apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic diagram illustrating a system configuration of an interactive information service according to an embodiment of the present invention;
FIG. 3 is a schematic diagram illustrating a hardware configuration of an image and data display method and apparatus according to an embodiment of the present invention;
FIG. 4 is an explanatory diagram showing display pictures of an image and data display method and apparatus according to an embodiment of the present invention;
FIG. 5 is an explanatory diagram showing different display pictures of an image and data display method and apparatus according to an embodiment of the present invention;
FIG. 6 is an explanatory diagram showing different display pictures of an image and data display method and apparatus according to an embodiment of the present invention;
FIGS. 7A , 7 B and 7 C are explanatory diagrams showing different display pictures of an image and data display method and apparatus according to an embodiment of the present invention;
FIG. 8 is an explanatory diagram showing a display picture in a prior art image and data display method and apparatus;
FIG. 9 is a schematic diagram illustrating an external appearance of a remote controller of an image and data display method and apparatus according to an embodiment of the present invention;
FIG. 10 is an explanatory diagram showing conceptually a construction of transmitting images and data simultaneously;
FIG. 11 is an explanatory diagram showing conceptually another construction of transmitting images and data simultaneously;
FIG. 12 is an explanatory diagram showing a data model in an image and data display method and apparatus according to an embodiment of the present invention;
FIG. 13 is an explanatory diagram showing a data structure of an image and data display method and apparatus according to an embodiment of the present invention;
FIG. 14 is an explanatory diagram showing an overall processing of an image and data display method and apparatus according to an embodiment of the present invention;
FIG. 15 is an explanatory diagram showing a flow of processing of a display change-over unit;
FIG. 16 is an explanatory diagram showing a flow of processing of an image display unit;
FIG. 17 is an explanatory diagram showing a flow of competition solving processing;
FIG. 18 is an explanatory diagram showing a flow of overlay processing;
FIG. 19 is a schematic diagram illustrating an overall system in case where the present invention is applied to a method of providing advertisement in WWW on the Internet;
FIG. 20 illustrates a display picture of a WWW browser in a user terminal;
FIG. 21 is a flow chart showing processing in a contents server;
FIG. 22 is a flow chart showing processing in a user terminal;
FIG. 23 is an explanatory diagram showing a data structure of user individual information;
FIG. 24 is an explanatory diagram showing a data structure of an advertisement list; and
FIG. 25 is a diagram showing a conceptual structure of a home page.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
An embodiment of the present invention is now described with reference to the accompanying drawings.
FIG. 2 illustrates a system configuration of an interactive information service according to the present invention. The system includes a subsystem 102 on the side of the information provider, an information transmission media 101 and a user terminal 1 . As information transmission media 101 , broadcasting media such as terrestrials waves, satellite broadcasting 103 and CATV, network media such internet 104 and package media such as CD-ROMs 105 and DVD (Digital Video Disk) are considered. In the subsystem 102 on the side of the information provider, a module 109 processes various contents 110 such as images and data into structure suitable for the transmission media and defines links among the media. The links among the media means the reference relationship among information sent to the users by means of the transmission media. For example, access can be changed from an image produced by means of broadcasting media to data on a home page on the Internet or a CD-ROM related to the image. Information is sent from a broadcasting station 106 to the satellite broadcasting 103 , from an Internet server 107 to the Internet 104 , and from a package preparing subsystem 108 to the CD-ROM 105 . The user terminal 1 receives the information to refer thereto.
FIG. 1 is a functional block diagram schematically illustrating of the user terminal 1 . The user terminal 1 includes a body apparatus 2 , a display unit 3 and user input means 4 . The body apparatus 2 receives at least one image source 5 and at least one data 6 . A transmitting method of image and data and a structure of data are described later.
The body apparatus 2 can be divided broadly into a functional block 10 for selectively receiving an image and data relative to the image, a functional block 11 for displaying the image and the relative data is synchronized with each other, and a functional block 12 for accessing to an external resource such as the internet and the CD-ROM. First, the functional block 10 selects at least one image in an image selection unit 13 on the basis of a command from the user input means 4 . The selection is the same as usual selection of a channel in a television, while the present invention is characterized in that data relative to the image is selected at the same time as the selection of the image. For example, when it is assumed that the user selects an image A of the channel number 1 , data a and b relative to the image A are selected. Then, the image is sent through an image input unit 14 to an image and data combination unit 22 of the functional block 11 .
On the other hand, the relative data is sent through a data input unit 15 to a data selection unit 16 . The data selection unit 16 of the present invention is characterized to further select relative data on the basis of previously determined utilization condition 17 . For example, when it is assumed that the user is a man of 30 years old and the utilization condition 17 is registered to that effect, the relative data sent to the data selection unit 16 is compared with the utilization condition, so that the data a is selected. The condition of a plurality of kinds such as address, hobby, character and the like besides age and sex can be registered as the utilization condition. At the same time, since an identifier of each individual user is also registered, the identifier of the user is set in the utilization condition on the side of the relative data as information to be sent to only a particular user. With such structure, the information provider side can narrow the users down to provide information effectively and at the same time since the user side can refer to only data relative to the specific user himself, the efficiency of reference to information is increased.
At the same time, when the condition concerning utilization environment is registered, the display condition 18 of relative data is prescribed on the basis of the condition. For example, processing so that a display area of the relative data conforms to the size of the display screen is considered. Further, the method that the display condition is prescribed for each utilization environment condition and the user terminal side selects the prescribed condition such that the relative data conforms to a display condition a under a condition A.
It is necessary that the functional block 11 displays an image and data so that the user can understand the relationship of the image and the data. Accordingly, the functional block 11 provides display means of three kinds including: an image display unit 26 ; a combination display unit 27 ; and a data display unit 28 . Examples of pictures by the display means are described in detail with reference to FIGS. 4 to 7 . Briefly, the image display unit 26 displays an image mainly on the whole display screen. The combination display unit 27 displays an image and data together. The data display unit displays only data on the whole display screen. Further, display screens are changed over by means of a display change-over unit 29 in response to a command from the user input means 4 .
As far as the image display unit 26 outputs only an image to the display unit 3 , the relation of the image and data cannot be transmitted to the user. Accordingly, the present invention is further characterized by the provision of a synchronization control unit 21 and the image and data combination unit 22 in order to display data relative to a specific scene of an image by an icon or telop indicative of contents thereof on the image. Particularly, the image and data combination unit 22 includes data overlay processing 24 for combining to superpose an icon or telop on an image. The icon is used to show a kind of relative data. For example, the icon represents that the relative data is present information, limited information for members or the like. Further, the telop represents a headline of the relative data. It is desirable that contents of the telop can be understood at a glance like a big headline of a newspaper.
At the same time, a data editing unit 20 is provided in order to edit the icon and the telop in advance on the basis of the display condition 18 when the display condition 18 is prescribed in the relative data.
For example, when the size of a display screen is small, the size of the icon and the telop is also created similarly small and the length of the telop is created short. As described above, the icon and the telop can be used to notify the existence of the data relative to the image to the users plainly and effectively.
Through processing 25 in the image and data combination unit 22 displays an image as it is without superposing the icon and telop on the image. The through processing is used when there is no data relative to the image or when the user turns off display of the icon and telop.
The combination display unit 27 displays the image and the relative data together. The combination display method includes a method of superposing the image on the relative data by image overlay processing 23 , a method of superposing data on the image by the data overlay processing 24 , a method of dividing a display screen of the display unit 3 into an image display area and a data display area and the like. Examples of pictures are described with reference to FIGS. 4 to 7 . The present invention is characterized in that when relative data is present in a specific scene of the displayed image, the icon and telop are displayed to be superposed on the image in the same manner as the image display unit 26 and when the user inputs a command for data display, relative data is displayed in the data display area. A benefit is realized since the user can view images of continuous media continuously without disturbing the images by displaying data and can refer to relative data on the same display screen simultaneously.
The data display unit 28 displays only relative data. In this case, when the display condition 18 is prescribed, the data editing unit 20 processes and edits data so that the data conforms to the condition. The functional block 11 includes a data temporary memory area 19 , in which relative data selected by the data selection unit 16 is stored temporarily. The relative data is sent to each processing unit in response to a request from each display unit.
Relative data is described briefly. In the present invention, as the relative data, characters and images having a so-called link structure exist similar home page on the Internet. Operation on a data display picture corresponds to operation of following links. Accordingly, the functional block 12 includes a data operation unit 32 for designating a link destination and a data search unit 33 for searching for the link destination. Further, the present invention is characterized in that relative data is not only sent but also taken out from transmission media such as the Internet 104 and the CD-ROM 105 . Accordingly, the data search unit requests searching not only the data temporary memory area 19 but also an Internet access unit 34 and a CD-ROM access unit 35 for data in accordance with information relative to an access method of relative data. The Internet access unit 34 receives an URL (Uniform Resource Locator) of a home page on the Internet 104 and obtains the home page corresponding to the URL to store it in the data temporary memory area 19 . The CD-ROM access unit 35 has substantial identical processing, while since there is a possibility that an access method is different for each CD-ROM title, it is necessary to previously determine an access protocol to the CD-ROM used in the information service. In the embodiment, a home page is described as a representative of contents of data relative to images hereinafter.
FIG. 3 schematically illustrates a hardware of the user terminal 1 . The user terminal 1 includes the body apparatus 2 , the display unit 3 and the user input unit 4 . Further, the body apparatus 2 includes a central controller 111 , a memory unit 113 , a display control unit 114 , an input control unit 115 , a broadcasting receiving unit 116 , a disk control unit 117 and a communication control unit 118 connected to one another through a bus 112 . The memory unit 113 includes the data temporary memory area shown in FIG. 1 and stores a processing program and data therein. The display control unit 114 controls output to the display unit 3 . The input control unit 115 receives the command input from the user through the user input means 4 and sends the command to the central controller. The central controller interprets contents of the command and executes an instruction for realizing the command. The broadcasting receiving unit 116 receives images and data sent from a broadcasting station through an antenna 119 . The disk control unit 117 accesses data in package media such as the CD-ROM 15 or the like. Similarly, the communication control unit 118 accesses to various information sources such as home pages on the internet 4 and the like.
FIGS. 4 to 7 show the transition of display pictures of an embodiment according to the present invention.
The transition of pictures is described with reference to FIG. 4 as an example. First, only an image is displayed in a display picture 200 . When a time stamp is started during display of the image, the picture changes to a display picture 201 or 203 . Incidentally, the time stamp is a structure for relating a specific image scene to data relative to the scene and represents a time from a beginning of the related image scene to the termination thereof. When any command is not input by the user during the time stamp, the display picture 201 or 203 is returned to the display picture 200 .
An icon 202 representative of a kind of related data is displayed in the display picture 201 and a telop 204 representative of contents of related data is displayed together with the icon. The icon 202 and the telop 204 are included in the related data. The present invention is characterized in that the icon and the telop indicate that there is data related to the image scene. Further, in the present invention, since data classified or individualized for each user is displayed, it is characterized that the icon or the telop is used to notify a kind or contents of data to the user plainly. In this embodiment, whether the telop is displayed or not can be set by the information provider. In addition, there is a mode in which the user can turn off display of the icon and the telop so that the user enjoys the image without disturbing the image by the icon or the telop. However, there is related data which is desired to be necessarily notified to the user depending on contents of the related data and accordingly there is provided a forced display mode of the icon and the telop.
Next, in the state of the display picture 200 , when the user instructs to change over the display, the display is moved to a display picture 205 , so that a home page viewed last or a default home page is displayed. On the other hand, when the user instructs to change over the display in the state of the display picture 201 or 203 , the display is moved to a display picture 213 in which a home page 214 relative to the image is displayed. As described above, the embodiment is characterized in that when the change-over of the display is instructed during display of the icon or telop, the home page relative to the image scene is displayed.
Further, in the display pictures 205 and 213 , reduced image 207 of a currently selected image is displayed to be superposed on the home page. As described above the present invention is characterized in that the user can view the image continuously without disturbing the image by display of data and at the same time the user can refer to the relative data.
In addition, the reduced image 207 usually has the same function as the display picture 200 of the image. Accordingly, in the display picture 205 , when a time stamp is started, the display picture is moved to a display picture 9 in which a telop 211 and an icon 212 are displayed on a reduced image 210 . In this state, when the user instructs to change over the display, the display picture is then moved to the display picture 213 in which a home page synchronized with the image is displayed. In this manner, since the user can be notified that there is new data relative to the image during simultaneous display of the image and the relative data, the user can refer to the relative data immediately.
Next, when the display is instructed to be changed over again in the state of the display picture 205 , the display picture is moved to a display picture 215 in which the reduced image 207 disappears from the picture and only the currently displayed home page is displayed. Similarly, when the display is instructed to be changed over in the state of the display picture 209 , the display picture is moved to a display picture 218 in which the reduced image 210 disappears and at the same time a home page synchronized with the image is displayed. This display mode is suitable for the case where the user wants to view the home page without disturbing it by the image on the contrary to the combined display mode of the image and the home page. Incidentally, operation of the home page is made by a menu 208 . Further, when the display is instructed to be changed over again, the display picture is returned to the display picture 200 in which only the image is displayed.
The menu 208 has an item of “re-display of automatically preserved icon and telop”. That is, icons and telops viewed by the user until now are automatically preserved as a list and when there is an indication from the user, the list is converted into a home page format (that is, format of HTML (Hyper Text Markup Language) to provide it to the user. For example, when the indication to that effect is inputted in the display picture 215 , the display picture is moved to a display picture 217 . A list of icons and telops automatically preserved until now is displayed in the display picture 217 . In the present invention, it is supposed that there is a need that the user overlooks relative data while the user is full of enthusiasm about the image and the user wants to view the relative data again later, and the above function of displaying the list of icons and telops is provided to cope with such need. Further, when all of icons and telops are preserved, the capacity of the memory unit 113 becomes insufficient at any memory capacity. Accordingly, priority is given to the relative data so that unnecessary data can be eliminated from the data having the lower priority. For example, when it is assumed that the priority is determined in accordance with the cost required for provision of information, the data is eliminated in order of a lower cost.
As described above, the transition of pictures has been described with reference to FIG. 4 . There are three kinds of display pictures including the display mode of only the image, the combined display mode of the image and the home page and the display mode of only the home page. In FIG. 4 , the modes are changed in order of the image display mode, the combined display mode and the home page display mode and return to the image display mode. On the other hand, FIG. 5 shows a different example of display pictures of the present invention, in which the modes are changed in order of the image display mode, the home page display mode and the combined display mode. The transition of pictures of FIG. 5 is suitable for mainly viewing the home page. Similarly, FIG. 6 also shows a different example of display pictures of the present invention, while the picture example does not contain the combined display mode. In order to display the combined image and home page, it correspondingly cost. However, the picture example of FIG. 6 can suppress the cost low.
Further, as the combined display mode of the image and the data, there are some other picture examples as shown in FIGS. 7A , 7 B and 7 C. For example, in FIG. 7A , a display screen 230 is divided into two areas. One of the areas is defined as an image display area 231 and the other is defined as a home page display area 232 . In the image display area 231 , existence of a relative home page is notified by an icon 234 and a telop 233 . At this time, when the user instructs to change over the image, a home page 235 synchronized with the image is displayed in the home page display area 232 .
In FIG. 7B , a display screen 240 is divided into one home page display area 241 and three image display areas 242 , 243 and 244 . The user selects an image from the image display areas and when data relative to the image exists, the existence is indicated by an icon 245 and a telop 246 . A home page synchronized with an image B can be displayed in response to an input command for changing over the display.
FIG. 7C shows a display example in which it is assumed that there are a plurality of data relative to a specific image scene. An image 251 is displayed now and a list 252 of relative data such as titles of relative data is displayed. When the user selects relative data from the list, a pertinent home page 253 is displayed. As another display method in the case where there are a plurality of data relative to a specific image scene, there is a display method in which in the display picture 201 or 203 of FIG. 4 the display time of the icon and telop is time-divided among the relative data or all of icons and telops of the relative data are arranged on the picture.
Further, in FIGS. 4 to 7 A, 7 B and 7 C, it is premised that the existence of relative data is indicated to the user and the user selects data to be displayed. When the image and the relative data can be viewed on the same picture like the display picture 209 of FIG. 4 and the display pictures of FIGS. 7A , 7 B and 7 C, there is a utilization form that display of the relative data is also changed automatically when a time stamp of the image is changed.
FIG. 9 shows a remote controller 260 of an example of the user input means in the present invention. The remote controller 260 includes a power button 261 , a channel change-over button 262 , a volume change button 264 , a channel direct selection button group 263 and the like in the same manner as a usual television remote controller. The present invention is characterized in that the remote controller 260 includes a display change-over button 265 and a home page display button 266 . The display change-over button controls the transition of states by the change-over of display in the display pictures of FIG. 4 . That is, when the user pushes the display change-over button, the display picture moves among the display pictures of FIG. 4 . Further, in FIG. 4 , the transition from the display picture 209 to the display picture 213 and the transition from the display picture 201 or 203 to the display picture 218 are performed by the home page display button 266 .
Further, in this embodiment, since processing for designating a link destination in the home page is required, cross keys 267 , 268 , 269 and 270 for moving a cursor up and down and right and left and a decision button 271 are provided. In the embodiment, the cross keys are used not only to designate a link destination in the home page but also to select relative data desired to be viewed by the user among a plurality of data relative to a specific image scene, for example, when the relative data are displayed as a list as shown in FIG. 7 C. The cursor may be moved by different means other than the cross keys. Further, selection may be made without using the cursor.
FIG. 10 shows arrangement of simultaneous transmission of image and data in terrestrial wave. Images are usually sent for each image frame 280 in surface wave, while an area 281 named a VBI (Vertical Blanking Interval) for taking synchronization in the vertical direction is provided between frames. Recently, it is permitted that empty portion of this area can be used for the data broadcasting. Data 282 are embedded in the area 281 in the broadcasting station and the data are taken out in the user terminal.
FIG. 11 shows arrangement of data broadcasting in the digital satellite broadcasting.
In the common analog satellite broadcasting, one transponder of a satellite is used to transmit one channel. However, in the digital satellite broadcasting, the image compression technique and the data multiplexing technique can be used to transmit images for four programs per transponder. At the same time, since some empty areas can be produced, this areas can be used to transmit data to the user terminal. At present, these areas are used to transmit a program guide or the like.
FIG. 12 illustrates a data model of relative data in the present invention. Data 291 holds a utilization condition 291 which prescribes users who can refer to the data. At the same time, the data has a time stamp 293 to be able to specify a related image scene 292 . Further, the data holds an icon 294 and a telop 295 displayed to be superposed on an image in order to notify the existence of relative data to the user. At the same time, the data holds data contents 296 or an access method to data entity.
The above data structure is materialized as shown in FIG. 13 . That is, data is managed by an identifier (id) number and includes: an image identifier (id); a utilization condition; a starting time; an end time and a duration of a time stamp; an image expressive of an icon; a character string displayed as a telop; and data contents. The image identifier (id) represents an identifier of a program image and uses a G code, for example. Further, an image scene related to data can be specified by the image identifier (id) and the starting time and the end time of the time stamp. As the utilization condition, an attribute value is set for each of previously determined attributes.
For example, the priority for selecting one of a plurality of relative data corresponding to one image is also included as one of the attributes. Alternatively, when the data is individualized, an identifier of the user is stored in this area. With regard to data contents, there is a possibility that the data is present in a home page on the Internet or a CD-ROM. In this case, an access method to the data is stored in the area.
A processing flow chart for implementing the image and display method of the present invention is now described with reference to a PAD diagrams shown in FIGS. 14 to 18 . Programs corresponding to processing shown in FIGS. 14 to 18 can be stored in a memory medium such as a floppy disk and be read in a memory upon start of the programs to be executed. The memory medium may store the programs and is not limited to a floppy disk.
FIG. 14 shows a processing flow of a main program 300 in the image and data display method. First, in step 301 , it is detected that the user pushes the power button 261 of the remote controller 260 to turn on a switch. In step 302 , a channel used when the switch was turned off last time is displayed. This processing in step 302 corresponds to processing in the image display unit and is described later. In step 303 , processing in steps 304 and 305 is repeated until the switch is turned off. In step 304 , a button of the remote controller 260 operated by the user is detected. In step 305 , processing corresponding to each button is performed. When the display change-over button 265 is selected, processing 306 in the display change-over unit is performed.
Next, when the home page display button 266 is selected, home page display processing 307 is performed. In the home page display processing, the mode is moved to the data display mode when the existence of relative data in the image display mode is indicated by an icon and a telop in FIG. 4 and data synchronized with the image is displayed. Similarly, in the combined display mode, when a telop and an icon are displayed in the reduced image picture and the existence of relative data is indicated to the user, the display is changed over to a home page synchronized with the image in the combined display mode. Next, when the channel button 262 or the channel direct selection button group 263 is selected, processing 308 in the image selection unit 13 is performed. The present invention is characterized in that data relative to the image is also changed over differently from change-over of the channel of the usual television.
A data operation button means the cross key having the buttons 267 to 271 . When the data operation button is selected, processing 309 in the data operation unit is performed. For example, the processing includes processing that a link destination on the home page is designated. Next, when the power button 261 is selected, the program 300 detects switching off and escapes from a loop 303 . In step 311 , a channel upon switching off is recorded so as to be able to display a television program immediately upon switching on next time.
In step 312 , the program is terminated. Operation such as, for example, adjustment of volume is considered else, while such operation departs from the gist of the present invention, it is omitted.
FIG. 15 shows a processing flow 306 in the display change-over unit 29 . First, in step 321 , a display mode at the present time is detected. In the embodiment, as shown in FIG. 4 , there are three kinds of display modes including: the image display mode; the combined display mode of image and data; and the data display mode. In step 322 , when the current display mode is the data display mode, processing 302 in the image display unit 26 is performed and the mode is moved to the image display mode. When the current mode is the image display mode, processing 323 in the combined display unit 27 is performed and the mode is moved to the combined display mode. When the current mode is the combined display mode, processing 324 in the data display unit 28 is performed and the mode is moved to the data display mode. Finally, in step 325 , the processing 306 is terminated.
The processing 324 of the data display unit in the embodiment is processing for displaying a home page. In the processing 323 of the combined display unit 27 , display of a home page relative to an image scene is prepared on a rear side of the image upon change-over of the picture. In this case, when there is no relative data, display of a finally viewed home page or default home page is prepared. After the completion of preparation, the image display area is reduced successively and at the same time the data display area is viewed to the user successively. The reason why animation or the like is used such that the image display area is reduced successively is that it is prevented that the user feels that it is difficult to understood since display of image and data is divided in a moment.
FIG. 16 shows a processing flow 302 in the image display unit 26 . The method of FIG. 10 is considered as the arrangement of the simultaneous transmission of image and data. Since data is stored for each frame of the image, it is necessary to take out the data for the frame unit. Steps 331 to 344 are repeated every predetermined period (in the embodiment, every one frame unit) in step 330 .
First, in step 331 , one frame image is input in the image input unit. In next step 332 , data embedded between frames is extracted. Since it is considered that data is not embedded, whether data is present or not is determined in step 333 and when data is present, steps 334 to 338 are performed. Processing in step 334 corresponds to processing of the data input unit 15 and in step 334 data is extracted to be decoded. Processing in step 335 corresponds to processing in the data selection unit 16 and in step 335 the registered utilization condition is collated with the utilization condition in the data. In next step 336 , when both the utilization conditions are coincident with each other, the data is stored in the temporary memory area 19 in step 337 . When both the utilization conditions are not coincident, the data is not stored in step 338 . In step 335 , the display condition of data such as a size of the icon and a font size of the character string is prescribed on the basis of the condition of utilization environment such as a size of picture screen. Since an amount of data received in one frame unit is not so much, operation that data is divided to be sent is considered. In this case, it is necessary to combine data divided for each segment to unify the data after the data preserving processing 337 .
Processing in next step 339 corresponds to processing in the synchronization control unit 21 and in step 339 , data corresponding to the current time zone in the currently displayed television program is retrieved. When the data structure of FIG. 13 is examined, the identifier (id) of the image and the time stamp are also previously prescribed and accordingly the identifier of the image and the time are compared with the identifier of the currently displayed image and the current time. In step 340 , when coincident data are present, steps 341 to 342 are performed and when coincident data are not present, step 343 is performed. In step 341 , since there is a possibility that a plurality of data are selected at the same time, processing for solving such conflict is required. After solving the conflict, in step 342 the icon and the telop are overlay-displayed on the image. Each processing is described in detail later.
Thereafter, the displayed icon and telop or the icon and telop which have low display priority and cannot be displayed are recorded. These icons and telops are converted into a home page in response to a request from the user and are prepared to be always accessed. In step 343 , since there is not pertinent data, the image is outputted to the display unit. In step 344 , the combined image of icon and telop or the image is displayed for one frame unit. Processing in steps 339 to 343 may be repeated every predetermined period. The processing in steps 339 to 343 is not necessarily required to be performed for each frame, while in the embodiment the processing is embedded in the loop 330 of one frame unit. When the mode is changed to the data display mode or when the switch is turned off, the processing is terminated in step 345 .
FIG. 17 shows a processing flow for conflict solving processing 341 . In step 350 , whether any other data relative to the same time zone is present or not is examined. In this embodiment, the case where a plurality of data is assigned in the same time zone is named the competition. As shown in FIG. 7C , when a list of relative data can be displayed in the form of list, the list of relative data may be displayed as it is, while when an icon and a telop indicative of contents of each individual relative data are displayed, it is necessary to decide an order of display, a display time and the like. Thus, whether there is a conflict or not is detected in step 351 and when there is no competition, the processing is terminated as it is (step 352 ). When there is a conflict, the display priority of data is determined and scheduling is prepared again so that the .icon and the telop are displayed in order of the priority. Finally, the processing 341 is terminated in step 354 .
FIG. 18 shows a processing flow of overlay display processing 342 . In step 360 , a display mode of icon and telop by the user and a forced display mode of icon and telop by the information provider are detected. When the forced display mode is on even if the display mode of icon and telop is off, data and a telop are forcedly displayed on the image to be overlapped on each other. Accordingly, in order not to perform the overlay processing, it is necessary to turn off the display mode of icon and telop and also turn off the forced display mode by the information provider. In step 362 , the icon and the telop are individualized for each user on the basis of the previously determined display condition. In next steps 363 and 364 , when the telop is present, processing 364 for superposing the telop on the image is performed. Similarly, in step 365 , when the icon is present, processing 366 for superposing the icon on the image is performed. The processing method of superposing a character string and a picture on the image conforms to the processing for superposing data on usual image to be displayed.
The embodiment of the present invention has been described laying stress on the broadcasting media, while the present invention can be used as the image and data display method using package media and communication media.
Next, a second embodiment in which the present invention is implemented in the utilization form in which contents on a network are provided together with information of goods such as advertisement or the like is described. More particularly, the present invention is applied to a method of providing information of goods in the WWW on the internet.
FIG. 19 is a schematic diagram illustrating an overall system of the embodiment. The system includes a contents server 400 and a user terminal 410 both of which are connected to the internet 415 .
The contents server 400 includes a WWW server 401 and an advertisement management program 403 , which are interlocked with each other by means of a CGI (Common Gateway Interface) conforming to the standard of WWW.
The WWW server 401 provides a home page 402 in response to a request from the user terminal 410 . As described above, in the embodiment, the home page constitutes contents.
The advertisement management program 403 manages advertisement and provides information 404 of goods suitable for the user. More particularly, an area (hereinafter referred to as an advertisement area) in which the advertisement can be displayed is previously ensured in the home page 402 and suitable advertisement is embedded in the area. Further, as described later, since user's individual information is sent from the user terminal 410 , suitable advertisement is selected on the basis of the user's individual information. At this time, when a plurality of information items of goods are selected, the display priority of each advertisement is prescribed and the advertisement is displayed in accordance with the priority.
The user terminal 410 includes a WWW browser 411 , a timer management program 412 , and an individual information management program 413 . The timer management program 412 and the information management program 413 prescribe inter-program interfaces with respect to the WWW browser 411 and are interlocked with the browser. Alternatively, it is considered that the WWW browser 411 includes the timer management program 412 and the information management program 413 , while the embodiment deals with the above structure.
The WWW browser 411 requires the home page from the WWW server 401 and receives the home page sent from the WWW server to be displayed.
The timer management program 412 manages the duration of display of each home page and sends a display request command of next information (in the embodiment, particularly, information of goods) to the WWW browser 411 every predetermined time. When the WWW browser 411 can cope with the request by the fact that information pertinent to the request is stored in a cache or a buffer, the WWW browser 411 copes to that extent and when it is necessary to make inquire to the server side, the WWW browser sends a command to the server.
The individual information management program 411 manages the user's individual information 413 and sends the individual information to the WWW server 401 through the WWW browser 411 if necessary. Since the WWW server 401 selects information of goods on the basis of the individual information, the individualized or classified information of goods is sent to the user.
The individual information is information concerning characters such as age, sex, address and the like and taste such as hobby, the likes of the user. There is considered implementation including: for example, (1) when the WWW browser makes inquiry to the WWW server, a network address of the user terminal is informed to the WWW server and accordingly this address is used as the individual information; (2) a file or program for taking custody of and managing the individual information is prepared separately; and (3) the individual information is managed by a third party agency collectively and the WWW server makes inquiry to the agency on the basis of the user's identifier. Particularly, in the above items (2) and (3), in many cases, the user previously decides the individual information which has no problem if it is opened to the public in view of protection of privacy. In this embodiment, implementation (2) is herein described.
The utilization image or outline of the embodiment is now described.
FIG. 20 shows a picture configuration of the WWW browser 411 in the user terminal 410 . The WWW browser 411 includes a window 420 having a menu 421 . The window includes an advertisement area 422 for displaying an advertisement (information of goods) 423 and a home page display area for displaying contents required by the user. Definitely, there is considered implementation such as (1) the window is divided into an area in which a home page by one HTML file is displayed and an area in which an advertisement is displayed, and (2) the advertisement 423 is also set as one home page and a frame tag of the HTML is used to display a plurality of home pages in one window. Further, in the case of (2), a parent home page for deciding an arrangement of the home page in the window is required, while it is assumed that the home page including the contents has the function of the parent home page and the home page for the advertisement is included in the home page for contents.
Generally, the advertisement 423 is often called a burner advertisement, while the present invention is characterized in that a plurality of advertisements can be displayed with respect to one home page and even if the home pages are identical, the advertisement is individualized or classified for each user. In other words, in FIG. 20 , even if contents displayed in the home page display area 424 are identical, there is a possibility that contents displayed in the advertisement area 422 are different for each user. Further, a plurality of advertisements are assigned to the home page 424 and the advertisement 423 in the advertisement area 422 is changed to another advertisement every predetermined time. Methods of displaying a plurality of advertisements, is implemented as (1) the duration for displaying one advertisement is provided as described above and advertisement is changed every time period, and (2) when the advertisement area 422 is sufficient, the advertisements are displayed as a list. In this embodiment, implementation (1) is discussed below.
The flow ( FIG. 21 ) of processing in the contents server is now described.
First, the WWW server 401 receives a content request command from the WWW browser 411 (step 430 ). Then, the command is analyzed to retrieve pertinent contents (step 430 ). As described above, in this embodiment, the home page constitutes the contents. Further, since the advertisement area has been previously provided in the home page and advertisement is embedded in the advertisement area by later processing, the retrieved contents are preserved temporarily.
Then, in step 432 , the WWW server 401 obtains individual information from the WWW browser 411 . Individual information is sent from the WWW browser together with the content request command, while generally the WWW server receives a content request command and request the individual information to the WWW browser.
FIG. 23 shows a data structure of the individual information. The individual information includes attribute values 462 for each user defined for previously prescribed attributes 460 . The individual information is managed as arrangement including a combination of attributes 460 and attribute values. The attributes 460 include characters such as age, sex and address and taste such as hobby, favorite music genre, favorite movie genre and kinds of favorite books of the user. The attributes are not required to be unified for each service and can be prescribed on the side of the user or the service provider newly. Further, since conventional or fixed information may be selected as the characters in inputting of the attribute values, a structure such as a pull-down menu which is easy to select the attribute values is adopted. In addition, a simple structure is adopted so that taste can be input by presenting questions to the user and accepting responses.
Next, the information-of-goods management program 403 retrieves information of goods coincident to the user's individual information and preserves the coincident information of goods temporarily (steps 433 to 436 ).
A list of advertisements as shown in FIG. 24 is used to retrieve information on goods. In the list of advertisement, the user's attribute of a target is prescribed for each advertisement ( 470 to 477 of FIG. 24 ). Items ( 480 to 486 of FIG. 24 ) of the attributes are the same as the individual information of FIG. 23 . Further, since the attribute values increase a width of the target user, a range or a plurality of attribute values are often input. For example, in advertisement 470 , the attribute of age 480 is prescribed to a range from 20 to 35 years old. In FIG. 24 , “Don't Care” means that the attribute value may be any value. That is, as the retrieval condition, reference is not made to the item of “Don't Care”. Further, although not shown in FIG. 24 , logical symbols such as “NOT”, “AND” and “OR” may be used to prescribe complicated conditions for each item.
In step 433 , an advertisement corresponding to the contents is first retrieved from the list of advertisements. As shown in FIG. 24 , since the list of advertisements include an item 487 in which URLs of home pages can be recorded, a pertinent advertisement is retrieved on the basis of the URLS. Since an advertisement relative to contents can be displayed by causing contents to correspond to advertisements, there is a merit that the appealing power of goods to the user can be increased. It is a matter of course that it is considered that specific contents do not correspond to THE advertisement.
Next, a vector matching to the received individual information of the user is taken for each advertisement. In vector matching, each advertisement and individual information are both regarded as sets (vectors) of attribute values and the degree of matching is calculated between the two vectors. As the calculation method, there are methods as follows: (1) whether the attribute value of the individual information is coincident with the condition of the advertisement list or not is calculated for each attribute item and the calculated results are ANDed; and (2) to what extent the attribute value of the individual information is coincident with the condition of the advertisement list is calculated for each attribute item and the calculated results are combined. In the embodiment, method (1) is described below.
In step 434 , when the advertisement is coincident with the individual information, the advertisement is temporarily preserved (step 435 ) and when the advertisement is not coincident with the individual information, operation proceeds to step 436 . The display priority of the advertisement preserved temporarily in step 435 is determined later. In step 436 , the processing is repeated for a next advertisement.
There are many cases where there are a plurality of advertisements coincident with the user's individual information. For example, in the case of FIGS. 23 and 24 , the advertisements 470 to 477 are coincident with all of the user's individual information. As described above, since the display area of advertisement has a limitation, all of advertisements cannot be displayed at a time. Accordingly, in the present invention the display priority is prescribed and advertisements are changed successively in accordance with the priority.
In step 437 , the display priorities among the temporarily preserved information for goods are determined. As definite methods, the following methods are used: (1) degrees of importance as previously determined among all advertisements and the display priorities conform to the degrees of importance, (2) when the vector matching of the user's individual information and the advertisement is taken, the degree of matching of both is calculated and the display priorities are determined in order of the degree of matching, and (3) the methods (1) and (2) are combined so that the degrees of importance degrees are weighted in accordance with the degrees of matching and the degrees of weighted importance are used as the display priorities. In this embodiment, method (1) is described below. Definitely, as shown in FIG. 24 , an item 487 of the degree of importance is provided in the advertisement list and the display priorities are determined in order of advertisements having higher degree of importance. For example, in FIGS. 23 and 24 , the display priorities are in order of advertisements 470 , 471 , 472 , 473 , 474 , 475 , 476 and 477 . Further, when the degree of importance are the same, the display priorities are determined on the basis of other factors, while in the embodiment, the display priorities are determined simply in order of description in the advertisement list.
The degree of importance corresponds to the advertisement charge. Accordingly, an advertisement of goods for which increased an advertisement charge is paid is displayed preferentially.
In next step 438 , the advertisements are embedded in the home page in order of priority. A conceptual structure of the home page in which advertisements are embedded is shown in FIG. 25 . The home page 490 includes a content portion 491 and advertisements arranged in order of the display priority. The reason the structure of the home page is described conceptual is that a home page generally has only information displayed simultaneously and when display of a part of the home page such as, for example, the advertisement area is desired to be changed, an inquiry is made to the server at any time. However, improvement of the current WWW can cope with the structure shown in FIG. 25 and accordingly in the embodiment description is made as it is.
Finally, in step 439 , the home page 490 is transmitted to the user terminal.
Next, the flow ( FIG. 22 ) of processing in the user terminal is described.
First, in step 450 , the WWW browser transmits a request command of the home page to the WWW server. At the same time, the WWW browser sends the individual information to the WWW server in cooperation with the individual information management program. The contents server receives the information and performs the processing shown in FIG. 21 . Accordingly, the WWW browser waits until the home page is completely received (step 451 ).
In next step 452 , the home page is displayed. At this time, the advertisement is also displayed in accordance with the display priority besides the contents. The display picture in this case is as shown in FIG. 20 , for example.
The processing in steps 453 and 454 are repeated at predetermined times. In step 453 , whether another advertisement is displayed or not is examined. Since the duration of display of each advertisement is previously prescribed, the timer management program examines the duration. When it is time to change the advertisement, operation is returned to step 452 in which only the advertisement is changed to an advertisement having a next display priority. Otherwise, operation is moved to step 454 .
When it is assumed that the duration also corresponds to the advertisement charge, the advertisement of goods to which the increased advertisement charge is paid can be displayed for a long time.
In step 454 , whether a request for changing contents is issued from the user is determined. When there is a request for changing contents, operation is returned to step 450 and the operation starting from the transmission of the content request command is repeated. Otherwise, operation returns to step 453 .
The method of providing the information of goods in the WWW on the Internet has been described, while the present invention is not limited to the Internet and the WWW and can be used in other communication media such as, for example, the communication using the personal computer.
According to the above embodiments, the existence of data classified or individualized for each user in relation to the displayed image scene can be presented to the user by the picture or character string indicative of contents of the relative data. At the same time, the relative data can be displayed synchronized with the image in response to a request of the user. In this manner, the possibility of accessing from the image to the relative data simply brings the information provider a benefit that the viewers are drawn in by a broadcasting image to move to the bidirectional media such as the Internet immediately. At the same time, the viewer can know detailed information relative to the image more simply. Further, since information suitable for the individual user can be sent directly, information can be provided and referred effectively.
Further, according to the embodiments, since the display condition and the display order of the picture and the character string indicative of the existence of the relative data are determined on the basis of the utilization environment condition, the existence of the relative data can notified to the user clearly and understandably.
Furthermore, in the embodiments, since there is provided the mode for displaying the image and the data simultaneously, access can be made to the image and the data freely to refer to information.
In addition, when the user inputs a command for displaying a list, a list of pictures and character strings displayed until now is displayed. When the user selects any one in the list, the relative data is displayed. Accordingly, the user can first view only the images continuously and refer to the relative data slowly later.
Moreover, in the embodiments, the number of relative data to be displayed as a list is limited and when the number of data exceeds the limitation, the data is selected in accordance with the priority. Accordingly, the memory area can be maintained to be small and consequently the cost of the terminal can be reduced.
Further, in the embodiments, since there is provided the mode for forcedly displaying the picture and the character string indicative of contents of the relative data, the intention of the information provider can be transmitted to the user of the target exactly.
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A device and method of displaying images and data on a display device. The device and method displays still and moving images in which at least one icon is associated and displayed with each image on a screen. A single screen may contain several images which change over time. As the images change so do the icons associated with them. Upon selection of an icon by a viewer, the device and method will display one of several possible advertisements or information associated with the icon. The selection of which advertisement or piece of information is based on information stored about the viewer. This information would include data concerning the viewer's age, income, address and hobbies. A list of selections made by a viewer is maintained and may be displayed at the viewer's request. The system may also force the display of advertisements if desired by advertisers.
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BACKGROUND OF THE INVENTION
1. Technical Field
This invention relates to a method and apparatus for mounting friction elements in disc brakes. A particular embodiment of the invention relates to the mounting of friction elements in a disc brake of the kind in which at least one brake disc is axially slideable with respect to its associated rotatable mounting and the friction elements which frictionally engage braking surfaces at opposite sides of the disc are slideably mounted on a fixed caliper or bridge structure which resists movement of the friction elements under the action of the frictional forces generated by engagement of same with the rotating brake disc during actuation of the brake. Certain aspects of the invention may find wider application than strictly in relation to a disc brake of the kind just enumerated.
2. Related Art
There is disclosed in WO 98/26192 and WO 98/25804 a disc brake of the kind described above in which resilient means is provided in relation to at least one axially slideable brake disc and in relation to at least one axially slideable friction element. The resilient means for the disc provides, inter alia, an anti-tilt mounting function. The resilient means for the friction element serves merely to prevent rattle.
In our above-identified prior published WO specifications, the arrangement adopted in relation to the friction elements for mounting the resilient means with respect to the fixed caliper or bridge structure has been on the basis of using the fixed and stable structure of the caliper or bridge as a mounting for providing the basis or foundation from which the resilient means takes its mounting for exerting the necessary forces on the friction elements. Such an arrangement has been considered a logical basis for the construction of an assembly in which there is a need for a high degree of structural and operational integrity achievable on the basis of, inter alia, simplicity of structure and assembly, and minimization of mechanical wear in use, and related factors.
In the embodiments of these prior proposals there has been adopted the use of a leaf-type spring acting from the caliper or bridge, and mounted thereon by means of fasteners, and a suitable connection to the friction elements accordingly.
One aspect of the construction of springing systems for the friction elements of spot-type disc brakes employing one or more axially floating discs, concerns the matching of the spring effect to the physical characteristics of the friction element concerned, notably the question of whether or not the friction element is double-sided (as occurs in the case of the central friction element between a pair of floating brake discs in a double-disc brake of this kind). There may be other circumstances in which it is desirable to vary the spring force applied to the friction element as between one such friction element between a pair of floating brake discs, the actual construction of the friction element (which affects its mass and inertia) differs from that of its associated single-sided friction elements on the outer side of each of the two brake discs. Likewise, it will be understood, that in addition to the static factors affecting such a friction element, so too the dynamic factors affecting it differ from those of its single-sided neighbors in that the double-sided frictional effects during actuation of the brake differ very substantially (from the single-sided effect) and lead to a requirement, we have discovered, for a differential springing effect as between the two types of friction elements accordingly.
While design or dynamic factors arising in a disc brake of the relevant kind may produce a requirement for a differential springing effect even in relation to a brake having a single sliding disc, as disclosed below and as is likely to be the case commercially, the more usual brake structure comprises at least two discs with a double-sided friction element slidingly mounted between the discs, and which is subjected to significantly different forces from those applied to its single-sided neighbor (on the piston-and-cylinder actuator side of the brake), and these differences lead to a requirement for the above-discussed differential springing effect.
Further related factors which have influenced the basis for the technical advance incorporated in the embodiments of the invention include the fact that our prior unpublished work in this field on the control of friction elements includes (as mentioned above) the use of leaf springs mounted on the fixed caliper of the disc brake and acting on all friction elements in an endeavor to provide the necessary spring effect in a simple structure. Such an arrangement can indeed be constructed to provide the required spring effect. However, improvements in several respects would be potentially capable of providing significant performance advantages in relation to such aspects as simplicity and cost of construction of the resilient means, simplicity of mounting (and the avoidance of the use of fasteners such as cap screws), avoidance of the entrapment of dirt and water, and the reduction of space requirements, with the related potential benefit in relation to vehicle turning circle as affected by the volume of movement described by the brake structure in vehicle turning movements (in relation to steered wheels). A further factor relates to ability to apply the spring effect at the location on the friction element where such is of best effect and preferably in a symmetrical manner, for example at both lateral sides of the friction element where it is mounted on guides for sliding movement towards and away from (at least in terms of relative movement) the associated disc friction surfaces.
SUMMARY OF THE INVENTION AND ADVANTAGES
The resilient means adopted in the embodiments of the present invention have a resilient effect and generate a corresponding spring force which is of a magnitude such that it is significantly greater than that which is required merely for elimination of rattle, and a distinction is therefore to be drawn between the resilient means of the embodiments of the present invention and previously proposed anti-rattle springs in brakes of various kinds. The spring forces generated in the embodiments of the present invention are at a level such that the friction elements are constrained (by the predetermined spring forces) from sliding on their guides, whereby not only is rattling or noise suppression achieved but also the friction elements are restrained from free sliding movement into contact with the brake discs in an uncontrolled manner.
In described embodiments of the invention, resilient means is provided by the two or more friction elements which are slideably mounted in a disc brake and the resilient means acts on both such friction elements so as to produce a differential resilient effect as between the two friction elements, whereby the resilient effect can be matched to the physical characteristics, including mountings, of the friction elements themselves.
In the described embodiments, the resilient means is adopted in a wire spring format which enables several significant advantages to be achieved, including simplicity of mounting (by means of cooperation between the wire of the spring and suitable drillings or bores or notches in the friction elements). Moreover the wire spring form conveniently enables the springs to incorporate various chosen profiles achieved by bending, whereby the location and geometry of the spring and its connection to the friction elements enables the required differential effect to be achieved. For example one simple way of effecting this is to arrange matters so that the moment of the forces exerted by the spring in relation to the friction element is varied in accordance with the required spring effect either by choosing the length of the moment arm accordingly and/or connecting the spring to the friction element appropriately.
Another aspect of the resilient means in the embodiment, which leads to practical advantages in relation to the general construction of the wire spring which provides the required resilient properties, is that a one-piece construction can be adopted which has a generally channel-shape profile as seen in its operating attitude in plan view and thus the wire spring is able to straddle the opposite sides of the caliper or bridge structure which supports the friction elements in their sliding movement. It will be understood that the adoption of a single wire spring construction enables the differing spring forces required by the friction elements to be applied at opposite ends of each of these. Moreover the spring construction has the inherent simplicity of a wire spring, and is coupled with the easy mounting of same as discussed above. Also the spring has the ability to extend between the spaced friction elements for actuation of each and the wire construction has an inherent tendency not to provide structures offering a trap for foreign matter and debris. In this way there has been provided a spring system for friction element mounting in brakes of the relevant kind which offers significant technical advances.
In the embodiments of the present invention the disc brake incorporates resilient means both in relation to the mounting of the brake discs on their mounting hub and in relation to the brake friction elements or pads in relation to their fixed mounting or caliper.
The resilient means are of a structure and strength chosen to be capable of, both in the case of the brake disc and in the case of the brake friction elements, maintaining these components of the brake assembly in their required working attitudes with respect to the structures on which they are mounted. In other words, the springs or resilient means for the brake discs are constructed so as to hold the brake discs in non-tilted working attitudes as they rotate. Likewise, the resilient means for the friction elements or pads maintain these latter structures in their required attitudes with respect to their fixed mounting or caliper. In both cases, the resilient nature of the resilient means permits under the dynamic conditions arising during use of the vehicle and due to engine vibration and vehicle motion/road surface induced vibration and similar factors, a degree of movement from the defined working position (as opposed to the linear axial sliding movement needed to effect friction element-to-disc engagement and disengagement when commencing and terminating braking) which is needed under normal conditions of vehicle use.
In this regard, it is to be noted that the resilient means or springs used in the embodiments in relation to the friction elements for maintaining same in their normal non-tilted attitudes, differ significantly from the springs disclosed in the above-identified WO 98/25804 and WO 98/26192 specifications in which the pad springs are mere anti-rattle springs not adapted to hold the brake pads against tilting movement, but merely to avoid rattling. Moreover, in the embodiments of the present invention the springs for the discs and for the pads are balanced in terms of their relative loading applied to the discs and the pads in order to achieve the necessary separation of same when braking is discontinued and yet holding the pads and discs against tilting during use. Thus, the spring forces exerted on the pads or friction elements of the present invention are much stronger than those merely to prevent rattling or noise suppression. The spring forces are sufficient to restrain the slideable brake pads or friction elements from moving into contact with the brake discs in an uncontrolled manner. The use of the substantially stronger pad springs in the present embodiment assists in positioning the outer rims of the brake discs in their brake-off position for reducing residual brake torque.
THE DRAWINGS
These and other features and advantages of the present invention will become more readily appreciated when considered in connection with the following detailed description and appended drawings, wherein:
FIG. 1 shows in block diagram format a spot-type automotive disc brake comprising a pair of axially slideable discs and associated friction elements, an actuating mechanism therefor and a fixed caliper or bridge structure overlying same;
FIGS. 2, 3 , 4 and 5 show views of a first embodiment of the invention which is applicable to a disc brake of the kind shown in FIG. 1, FIG. 2 being a perspective view of the caliper assembly which includes a central friction element and two side or end friction elements, and FIGS. 3, 4 and 5 being views of the resilient means or spring, on its own, as seen generally in the directions indicated in FIGS. 2 and 3 by arrows III, IV and V respectively;
FIGS. 6, 7 , 8 and 9 show a second embodiment of the invention which is likewise applicable to a disc brake of the kind shown in FIG. 1, FIG. 6 being a perspective view similar to that of FIG. 2 but showing a different form of spring and mounting which is adapted to act at one side only of the assembly of three friction elements, FIG. 7 being a side elevation view of the spring as seen in the direction of arrow VIII in FIG. 6, and on a somewhat larger scale; and
FIGS. 8 and 9 being further views of the spring of FIG. 7, as viewed in the direction of arrows VIII in IX in FIG. 7 .
DETAILED DESCRIPTION
As shown in FIG. 1 a spot-type automotive disc brake 10 comprises a pair of rotatable brake discs 12 , 14 , a rotatable mounting 16 for the brake discs to permit rotation of the discs and which is adapted to drive the brake discs and have exerted thereon the braking effect by the discs when the disc brake 10 is actuated.
Two pairs of friction elements 18 , 20 and 20 , 22 are provided and are adapted to frictionally engage braking surfaces 24 , 26 provided at opposite sides of brake discs 12 , 14 to effect braking on actuating actuation means for the brake. Central friction element 20 is double-sided for frictional engagement with the mutually-inwardly facing braking surfaces 24 , 26 of brake discs 12 , 14 and is provided with appropriately facing friction pad material accordingly. Friction elements 18 , 20 and 22 comprise (as shown in FIGS. 2 and 6) in each case a generally flat metal backing plate 28 and secured thereto and standing proud thereof a body of friction material 30 of known construction for high durability frictional engagement with the relevant braking surface of the relevant brake disc. In the case of central friction element 20 , the friction material is provided at both faces of the backing plate 28 .
Brake discs 12 , 14 are axially slideable in use with respect to their rotatable mounting 16 under the action of friction elements 18 , 20 , 22 and the actuation means (to be described below) therefor during braking. For example the brake discs may be keyed to the rotatable mounting or hub 16 at three or more locations and resilient means may act there between. We refer to the disclosure in our co-pending application numbers GB 0010810.0 and PCT/GB01/01958 (corresponding to co-pending U.S. application Ser. No. 10/019,919, filed contemporaneously herewith) and incorporate the relevant portion of the disclosure therein herein by reference accordingly.
A fixed non-rotatable mounting 32 for friction elements 18 , 20 and 22 is provided comprising a caliper or bridge structure 34 which is mounted on a fixed structure of the vehicle to be braked, for example on the wheel mounting and which straddles the brake discs 12 , 14 and also provides a mounting for actuation means 36 , 38 (indicated diagrammatically) which applies inwardly directed braking forces to the outer friction elements 18 , 22 , thereby causing frictional engagement with the brake discs 12 , 14 and slight sliding movement of those discs with respect to their rotatable mounting 16 . In FIG. 1 of course it can be seen that the clearances between the structures have been greatly exaggerated for simplicity of diagrammatic illustration. The actuation means 36 , 38 could comprise a pair of piston and cylinder assemblies. However only one such is strictly needed since the actuation means can be one-sided with a fixed structure at one side or the other of the assembly of discs and friction elements (which fixed structure could simply be a stop extending from caliper 34 ), and against which fixed structure the assembly is pushed by the single actuation means.
Fixed and non-rotatable mounting 32 for the friction elements 18 - 22 is adapted permit sliding movement of the friction elements into and out of frictional engagement with the brake discs while resisting rotational movement of the friction elements under the action of frictional forces generated by engagement of the friction elements with the discs 12 , 14 . As shown in FIGS. 2 and 6 the friction elements are slideably mounted on the caliper 34 by means of a pair of laterally-facing guide rails 40 provided one at each side of the caliper 34 , and complementarily-shaped grooves formed in the friction element backing plates 28 whereby these latter are freely slidingly movable on the rails 40 , with a minimum of clearance or backlash, having regard to acceptable manufacturing tolerances.
Resilient means 44 is provided in relation to the non-rotatable mounting 32 for the friction elements 18 - 22 and is adapted to act between the friction elements (at the opposite sides of the brake discs) and caliper 34 in order to minimize friction element movement in the brakes-off condition and/or noise and/or rattle with respect to the caliper or bridge 34 (and generally in a direction laterally with respect to the direction of inward movement of the friction element to engage the brake discs on commencing braking), as will be more fully described below.
Turning now the construction of resilient means 44 , in the embodiment of FIGS. 2-5, this is adapted to act on all three friction elements 18 , 20 and 22 and so as to exert a differential spring effect as between the central one 20 of these and the other two friction elements 18 , 22 , by virtue of differential physical characteristics in the connection of the resilient means to the friction element 20 and to the friction elements 18 , 22 accordingly.
As will be explained below, resilient means 44 is constructed and arranged so as to exert its differential spring effect on the friction elements 18 , 20 and 22 by being connected to these at different locations on the friction elements at which the resilient means generates different levels of force. Moreover the resilient means 44 is in the form of a wire spring which is caused to exert its differential spring effect by virtue of shaped portions of the wire spring in which the wire follows a non-linear profile, as more fully described below.
In this first embodiment of the invention, resilient means 44 extends generally axially with respect to the brake discs 12 , 14 in axial portions 46 , 48 of the resilient means (see FIG. 3) and has laterally-extending portions 50 , 52 at the ends of the axial portions, the latter of which extends across to and is joined integrally with the other such portion 52 so as to form with a U-shaped overall spring structure which cooperates with the friction elements 18 , 20 and 22 at opposite (circumferentially-spaced with respect to the brake disc) sides of each friction element.
It will be understood that in this embodiment of a fixed caliper/floating disc-type disc brake the actuation of the brake is in fact effected from a piston and cylinder assembly (not shown) at one side only (say actuation means 36 ) so that friction element 22 is simply fixed to caliper 34 and does not require to slide with respect thereto. Thus, only central friction element 20 and floating friction element 18 require the action of resilient means 44 .
Accordingly, turning now to the details of the construction and arrangement of resilient means 44 in FIGS. 2-5, it will be seen in FIG. 2 that the resilient means is constructed in the form shown in FIGS. 3, 4 and 5 of a wire spring.
As can be seen in FIG. 2, wire spring 44 engages the undersides of guide rails 40 of caliper 34 at the inner end of laterally extending portions 50 of the spring and extends via bends 56 , 58 , 60 , 62 , 64 , 66 and 68 to the transverse proportion 70 which is an integral link between the laterally-extending portions 52 .
Wire spring 44 acts on sliding friction elements 18 , 20 at notches 72 , 74 , between which the wire is jogged whereby the spring force within spring 44 is applied to the friction elements at different locations thereon (with respect to guide rails 40 ), and indeed at different portions of the spring which have differing geometry with respect to the overall spring structure and thus themselves give rise to a differential spring effect.
In the embodiment of FIGS. 6-9, the general construction of the caliper assembly is similar to that of the preceding embodiment. In FIG. 6, the direction of viewing is different from that of FIG. 2, the caliper assembly being viewed from the actuation side, looking towards the fixed friction element 22 , item 76 being a housing for the hydraulic actuator assembly. In this embodiment, instead of providing a single spring assembly joined by transverse portion 70 as in the embodiment of FIGS. 2-5, a pair of springs 78 are provided one associated with each of the guide rails 40 and which are located by an end spigot 80 which locates in a bore in fixed friction element 22 , the other end of each spring 78 engaging the underside of guide rails 40 , as in the preceding embodiment, and the spring engaging in notches 72 , 74 formed in the friction elements in a manner similar to that of the preceding embodiment.
It will be noted that in both of the above embodiments, the resilient means 44 are constructed to be able to accommodate the limited axial sliding movement of the friction elements with respect to the caliper 34 in use by means of sliding movement of the friction elements with respect to linear portions of the wire spring elements.
Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described. The invention is defined by the claims.
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A spot-type automotive disc brake of floating-twin disc and fixed-caliper format utilizes one or more single wire springs to bias the two floating friction elements with respect to the fixed caliper. Each spring exerts a differential resilient effect on the central friction element with respect to the floating side friction element by virtue of differential connection arrangements, thereby meeting the differential springing requirements.
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FIELD OF THE INVENTION
The invention concerns processes for purifying aromatic amino sulfonic acid compounds and to high performance dyes produced from the purified aromatic amino sulfonic acid compounds.
BACKGROUND OF THE INVENTION
Many dyes, as well as pigments, are prepared by a two-step process of diazotization of an aromatic amino compound followed by coupling of the product. In certain applications, such as when the dye is used in an aqueous ink for inkjet printers, it is desirable to exclude, so far as possible, any impurities such as salts. Salt impurities in aqueous inkjet printer inks tend to promote the corrosion of the metal parts of an inkjet printer. In addition, salt impurities in certain aqueous ink compositions may tend to destabilize the ink components, causing the ink components to precipitate.
Hinson et al., U.S. Pat. No. 4,617,381 discloses a process for preparation of Cl Direct Yellow 11 in which the tetrasodium salt is acidified with sulfuric acid to a pH of less than 2.5, then heated. The salt is then neutralized to a pH of 6.0 to 7.5 with an alkanolamine to precipitate the alkanolamine complex. The free acid form is disclosed as having extremely poor filtration characteristics, as the salts formed by neutralization with either sulfuric or hydrochloric acid form a viscous slime that could not be filtered. The alkanolamine complex is reported to have improved stability.
Ono et al., U.S. Pat. No. 5,366,543 discloses preparation of a diazo dye salted with a substituted amine having at least one group of 6 to 12 carbon atoms. Two moles of sec-butylaniline are diazotized and then coupled with 1 mole of di-J acid (bis-(5,5'-dihydroxy-2,2'-naphythyl)amine-7,7'-disulfonic acid) or a similar coupling compound. The water-soluble dye product is salted with an amine having at least one group with 6-12 carbon atoms by mixing an excess of the amine with the water-soluble dye in aqueous solution for 2-5 hours in acidic or neutral atmosphere. When the amine is water-insoluble or has low solubility in water, the salt-formation step is carried out in an organic solvent such as an alcohol followed by addition of the solution into an aqueous acid solution, one example being aqueous acetic acid, to precipitated out the amine-salted dye. The precipitated dye is then filtered and rinsed with water.
Weberndoerfer et al., U.S. Pat. No. 4,560,745 discloses a process for preparing sulfonic acid functional dyes having low electrolyte content. An aqueous solution or suspension of the dyes is mixed with a water insoluble amine having 12 to 40 carbon atoms to separate the dye into a lipophilic phase; bringing the pH to less than 5 with an acid, for example sulfuric acid, and mixing the batch thoroughly, separating the phases, and mixing the lipophilic dye phase with a water soluble base and water to produce an aqueous solution of the dye.
Bermes et al., U.S. Pat. No. 5,431,723 discloses a dye preparation that is essentially free of foreign salts. The dye is prepared by diazotizing 4,4'-diaminostilbene-2,2'-disulfonic acid and then coupling with 1-hydroxy-7-aminonaphthalene-3-sulfonic acid in alkaline medium. The coupled product is acidified with hydrochloric or sulfuric acid to precipitate the product dye. The precipitated product is filtered, washed with water or dilute hydrochloric acid, and dried.
While these references generally discuss purification of a dye product, it would be advantageous to have an improved method of producing an amino sulfonic acid compound-based dye by using a purified starting product. Some of the advantages to purifying the aromatic amino sulfonic acid starting material rather than the finished dye are that (1) the dye is often a form that is difficult to filter and wash, such as a tar-like lake; (2) there is less material that must be purified for the amino- and sulfonic acid-containing starting material as compared to the coupled dye; (3) material loss in the dye purification step is more expensive; and (4) there is no organic in the waste stream that would need more expensive disposal means.
SUMMARY OF THE INVENTION
According to the invention, an aromatic amino sulfonic acid compound is purified by a process including steps of:
(a) dissolving the aromatic amino sulfonic acid compound in aqueous medium having a basic pH;
(b) acidifying the aromatic amino sulfonic acid compound solution with acetic acid to precipitate the aromatic amino sulfonic acid compound; and
(c) removing the precipitated aromatic amino sulfonic acid compound from the aqueous medium.
It has been discovered that, while various acids are used for the purification of dyes as described above, acetic acid provides a marked and unexpected advantage in the purification of amino sulfonic acid compounds such as diamino stilbene disulfonic acid compounds that are used as starting materials for dyes and pigments.
DETAILED DESCRIPTION OF THE INVENTION
Compounds suitable for use in the process of the invention are aromatic compounds having one or more amine groups, preferably primary amine groups, and one or more sulfonic acid groups. The aromatic amino sulfonic acid compound has at least one aromatic ring and may have multiple rings. When the aromatic amino sulfonic acid compound has multiple aromatic rings, the aromatic rings can be fused or bridged. Examples of bridged aromatic rings include, without limitation, those bridged by an alkylene group (e.g., methylene or isopropylene) or by an amine group. In addition to the amine and sulfonic acid groups, the aromatic amino sulfonic acid compound can have other substituents, including, without limitation, alkyl groups and hydroxyl groups.
The amino sulfonic acid containing compound is dissolved in aqueous medium having a basic pH. Preferably, the aqueous medium has a pH of at least about 10. In a preferred embodiment the pH of the aqueous medium is adjusted to be from about 10 to about 12. The aqueous medium preferably contains water and a base such as sodium hydroxide, although the medium may contain other materials that would not interfere with the purification process.
The aqueous medium may be heated slightly, for instance to about 45 to 50° C., to obtain a complete solution of the aromatic amino sulfonic acid compound. The solution may be filtered if desired to remove insoluble impurities.
After the aromatic amino sulfonic acid compound has been completely dissolved, the compound is acidified with acetic acid. The pH of the aqueous medium is preferably brought within the range of about 4.5 to about 5.5, more preferably a range of about 4.8 to about 5.1. The aromatic amino sulfonic acid compound should be essentially completely precipitated by the acetic acid. By "essentially completely precipitated" it is meant that the amount of the aromatic amino sulfonic acid compound remaining in the aqueous medium is less than about 2%, preferably less than about 1%, and even more preferably less than about 0.75% by weight of the total weight of the aromatic amino sulfonic acid compound. If more aromatic amino sulfonic acid compound remains in the aqueous phase than desired, additional acetic acid can be added incrementally to achieve more complete precipitation.
The precipitated aromatic amino sulfonic acid compound is separated from the aqueous medium by filtration. The collected solid material is washed with warm water. The water is advantageously at a temperature of at least about 35° C. A convenient temperature range for the wash water is from about 35 to about 45° C. or, more preferably from about 35 to about 40° C. The precipitated aromatic amino sulfonic acid compound is washed with the warm water until the conductivity of the filtrate indicates that essentially all of the soluble salts have been removed. Typically, the washing may be continued until the filtrate has a conductivity of less than about 500 micromhos, and preferably a conductivity of less than about 400 micromhos.
The precipitated aromatic amino sulfonic acid compound recovered preferably has a concentration of sulfate ion of less than about 400 ppm and more preferably less than about 200. The precipitated aromatic amino sulfonic acid compound recovered preferably has a concentration of chloride ion of less than about 100 ppm and more preferably less than about 80 ppm.
The purified aromatic amino sulfonic acid compound is advantageously used in the production of a pigment or dye compound by a two-step process of diazotization followed by coupling of the product. A purified aromatic amino sulfonic acid compound may be the diazotized compound, the coupler, or both.
Examples of suitable aromatic amino sulfonic acid compounds for diazotization include, without limitation, diamino stilbene disulfonic acids, including 4,4'-diaminostilbene-2,2'-disulfonic acid; bis-triazinyl-aminostilbenedisulfonic acids, including unsubstituted or alkoxy or amino substituted bis-triazinyl-4,4'-diaminostilbene-2,2'-disulfonic acid compounds; sulfanilic acid; amino benzene sulfonic acids, such as 1-amino-2-methyl-4-benzenesulfonic acid; amino-azobenzene sulfonic acids, such as 4-amino-azobenzene-4'-sulfonic acid; and so on.
The diazotized compound may be coupled using a conventional coupling process. Examples of compounds known to be suitable couplers include, without limitation, β-napthol, gamma acid (7-amino-1-hydroxynaphthalene-3-sulfonic acid), H-acid (8-amino-1-hydroxynaphthalene-3,6-disulfonic acid), I-acid, J-acid, di-J acid (bis-(5,5'-dihydroxy-2,2'-naphthyl)amine-7,7'-disulfonic acid), 2-hydroxy-3-methylbenzoic acid, and so on.
The dyes produced according to the invention may be used in ink jet printer inks where the absence or extremely low levels of salt impurities is beneficial because of the tendency of such salts to corrode the metallic parts of the ink jet printer.
The invention is further described in the following example. The example is merely illustrative and does not in any way limit the scope of the invention as described and claimed. All parts are parts by weight unless otherwise noted.
EXAMPLE 1
A suitable container is charged with 130 grams of water. While stirring, 15.4 grams of caustic (39% aqueous sodium hydroxide, 0.15 moles) is added slowly. Next, 30 grams (0.081 mole) of 4,4'-diaminostilbene-2,2'-disulfonic acid having a purity of 97%, 1320 ppm sulfate, and 240 ppm chloride is added with high stirring. Stirring is continued for about 10 to 15 minutes. The pH is then adjusted to 10-12, if necessary and the mixture is heated to about 45 to 50° C. to obtain a complete solution.
The solution is then acidified with 20 grams (0.33 mole) of acetic acid. The acidified solution is stirred for 30 to 35 minutes, at which time the pH should be in the range of from about 4.8 to about 5.1 and the 4,4'-diaminostilbene-2,2'-disulfonic acid should be completely precipitated, leaving less than about 0.7% by weight of the 4,4'-diaminostilbene-2,2'-disulfonic acid in the aqueous phase. The aqueous phase can be analyzed for the presence of the 4,4'-diaminostilbene-2,2'-disulfonic acid, and additional acetic acid is added in increments of one gram, if necessary, with additional stirring, to remove additional 4,4'-diaminostilbene-2,2'-disulfonic acid.
The mixture is filtered. The collected 4,4'-diaminostilbene-2,2'-disulfonic acid is washed with 400 grams water at 35 to 40° C. The wash with 35-40° C. water is repeated as necessary until the conductivity of the filtrate is less than about 400 micromhos. The collected 4,4'-diaminostilbene-2,2'-disulfonic acid is then removed from the filter and dried.
The yield is 86.0%. The 4,4'-diaminostilbene-2,2'-disulfonic acid has a measured purity of 96%, 120 ppm sulfate ion, and 56 ppm chloride ion.
COMPARATIVE EXAMPLE A
A suitable container is charged with 130 grams of water. While stirring, 15.4 grams of caustic (39% aqueous sodium hydroxide, 0.15 moles) is added slowly. Next, 30 grams (0.081 mole) of 4,4'-diaminostilbene-2,2'-disulfonic acid having a purity of 97%, 1320 ppm sulfate, and 240 ppm chloride is added with high stirring. Stirring is continued for about 10 to 15 minutes. The pH is then adjusted to 10-12, if necessary and the mixture is heated to about 45 to 50° C. to obtain a complete solution.
The solution is then acidified with 21.5 grams (0.19 mole) of hydrochloric acid. The acidified solution is stirred for 30 to 35 minutes, at which time the pH should be in the range of from about 4.8 to about 5.1 and the 4,4'-diaminostilbene-2,2'-disulfonic acid should be completely precipitated, leaving less than about 0.7% by weight of the 4,4'-diaminostilbene-2,2'-disulfonic acid in the aqueous phase. The aqueous phase can be analyzed for the presence of the 4,4'-diaminostilbene-2,2'-disulfonic acid, and additional hydrochloric acid is added in increments of 0.5 gram, if necessary, with additional stirring, to remove additional 4,4'-diaminostilbene-2,2'-disulfonic acid.
The mixture is filtered. The collected 4,4'-diaminostilbene-2,2'-disulfonic acid is washed with 400 grams water at 35 to 40° C. The wash with 35-40° C. water is repeated as necessary until the conductivity of the filtrate is less than about 400 micromhos. The collected 4,4'-diaminostilbene-2,2'-disulfonic acid is then removed from the filter and dried.
The yield is 86.5%. The 4,4'-diaminostilbene-2,2'-disulfonic acid has a measured purity of 96.5%, 466 ppm sulfate ion, and 3459 ppm chloride ion.
COMPARATIVE EXAMPLE B
A suitable container is charged with 130 grams of water. While stirring, 14.7 grams of caustic (39% aqueous sodium hydroxide, 0.15 moles) is added slowly. Next, 29.5 grams (0.08 mole) of 4,4'-diaminostilbene-2,2'-disulfonic acid having a purity of 97%, 1320 ppm sulfate, and 240 ppm chloride is added with high stirring. Stirring is continued for about 10 to 15 minutes. The pH is then adjusted to 10-12, if necessary and the mixture is heated to about 45 to 50° C. to obtain a complete solution.
The solution is then acidified with 19.7 grams (0.20 mole) of sulfuric acid. The acidified solution is stirred for 30 to 35 minutes, at which time the pH should be in the range of from about 4.8 to about 5.1 and the 4,4'-diaminostilbene-2,2'-disulfonic acid should be completely precipitated, leaving less than about 0.7% by weight of the 4,4'-diaminostilbene-2,2'-disulfonic acid in the aqueous phase. The aqueous phase can be analyzed for the presence of the 4,4'-diaminostilbene-2,2'-disulfonic acid, and additional hydrochloric acid is added in increments of 0.5 gram, if necessary, with additional stirring, to remove additional 4,4'-diaminostilbene-2,2'-disulfonic acid.
The mixture is filtered. The collected 4,4'-diaminostilbene-2,2'-disulfonic acid is washed with 400 grams water at 35 to 40° C. The wash with 35-40° C. water is repeated as necessary until the conductivity of the filtrate is less than about 400 micromhos. The collected 4,4'-diaminostilbene-2,2'-disulfonic acid is then removed from the filter and dried.
The yield is 87.0%. The 4,4'-diaminostilbene-2,2'-disulfonic acid has a measured purity of 93%, 16,000 ppm sulfate ion, and 68 ppm chloride ion.
The Example 1 method of the invention thus produces a product having a marked reduction in corrosive salt impurities over the products of the Comparative Examples A and B methods.
The invention has been described in detail with reference to preferred embodiments thereof. It should be understood, however, that variations and modifications can be made within the spirit and scope of the invention and of the following claims.
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An aromatic amino sulfonic acid compound is purified by a process including steps of:
(a) dissolving the aromatic amino sulfonic acid compound in aqueous medium having a basic pH;
(b) acidifying the aqueous medium with acetic acid to precipitate the aromatic amino sulfonic acid compound; and
(c) removing the precipitated aromatic amino sulfonic acid compound from the aqueous medium.
Using acetic acid in the process results in removal of more impurities and undesirable sulfate and chloride salts to provide an improved material for synthesizing dyes and pigments.
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FIELD OF THE INVENTION
[0001] The invention relates to an under deck fastening clip, system and method which can be used to “invisibly” attach a structural member to a supporting joist-like structure.
BACKGROUND OF THE INVENTION
[0002] There are a variety of decking systems on the market today. Most of the decking systems utilize some sort of fastening means to attach the structural members to the underlying joists such as a screw, nail or staple. Typically, the fastening means is installed directly through the top face of the structural members to the joist below.
[0003] The common method of securing the structural members to the underlying joists by directly fastening the structural member to the joist through the top face of the structural member has many drawbacks. First, the fasteners are visible, unattractive and take away from the façade or look of the natural wood. The fasteners may rust and discolor the structural members. A fastener may work loose and become a safety hazard to persons walking on top of the supporting structure. Finally, hammer blows to decking surface during installation of the fastener may cause damage and/or depressions that collect water. The collection of water may lead to splintering of the structural members, mold growth and the propagation of cracks starting at where the fastener installation occurs.
[0004] Another problem associated with the above is the potential for error during installation of the structural members because the installer cannot see exactly where the joists lie underneath the structural member. Resultantly, during installation of fasteners the installer may miss a joist or only partially strike a joist with the fastener and may have to back out the fastener or leave the fastener in the structural member and install yet another fastener to secure the structural member to the joist.
[0005] Another shortcoming is the potential for the structural members to loosen and move over time losing its uniform look resulting in loss of aesthetic appeal. In addition, the structural members may move to close the gaps between the installed structural members. The gaps between structural members are necessary to provide a means for rainwater or other liquids to drain from the supporting structure and for ventilation.
[0006] As a consequence of the foregoing, different types of fastening clip devices have been proposed to secure the structural members to the supporting structure invisibility without disturbing the appearance of the deck surface. According to the present invention an improved clip device is proposed which is easy to manufacture and simple to use. Additionally the clip device prevents lateral movement of structural members relative to one another and is designed to accommodate expansion and contraction forces to which the structural members are subjected by nature.
SUMMARY OF THE INVENTION
[0007] One object of the invention is to provide a system wherein the structural members are easy to install and wherein the structural members can be installed and maintained without access to the underside of the structural members.
[0008] Another object of the present invention is to provide a system wherein the structural members can be installed without the penetration of the top surface of the structural member with a fastener.
[0009] Another object of the present invention is to provide a decking installation system, method and clip with a cost effective means of manufacture and installation.
[0010] Another object of the present invention is to eliminate the need to use spacers during installation while maintaining the required consistent spacing among the structural members during installation.
[0011] Another object of the invention is to provide a clip which facilitates and accommodates the lateral expansion of the structural members and prevent their longitudinal movement with reference to the clip.
[0012] According to yet another object of the invention, the clip according to this invention is generally a Π-shaped clip device having a top horizontal portion and a pair of integrally formed spaced apart vertical legs underneath. The legs define a spacing distance across their span and are inwardly compressible toward each other in response to a side force. The top or bottom surface of the top portion has raised gripping means for frictionally engagement. The side edges of the horizontal portion are inserted into the grooves of adjacent structural members to abut against said legs to thereby engage and secure the structural members to a supporting structure separated from each other by the spacing distance.
[0013] Further features of the invention will be described or will become apparent in the course of the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] In order that the invention may be more clearly understood, embodiments thereof will now be described in detail by way of example, with reference to the accompanying drawings, in which:
[0015] FIG. 1 is an isometric view of a clip device according to the present invention;
[0016] FIG. 2 is a side view of a clip device according to the present invention;
[0017] FIG. 3 is a side view of a structural member according to the present invention.
[0018] FIG. 4 is a side schematic view of a decking system according to the present invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0019] Referring to FIG. 1 , a generally Π-shaped clip device 1 according to the present invention is illustrated. The clip is intended to be used in conjunction with structural members 8 or planks which are manufactured with longitudinal grooves or slots 9 on each opposing side edge as shown in FIG. 5 . As will be described hereafter, the clip device 1 is securely fastened to the surface of a supporting surface such as an underlying joist 10 and serves as an anchoring device to secure adjacent structural members 8 in place.
[0020] Referring to FIG. 3 , grooves 9 are provided in the opposing side edges of the structural members 8 . The groove has a thickness t and divides the side edge into a top and bottom edge portion. The groove functions to receive the clip during installation of the decking system. The structural members 8 may be manufactured from a non-wood material such as PVC or composite materials, or alternatively, traditional wood structural members modified with grooves may also be used.
[0021] Referring to FIGS. 1-4 , the clip device 1 may be made from any material that is suitable. In the preferred embodiment the clip device 1 is manufactured from a durable plastic material. The clip device 1 comprises a top horizontal portion 2 that is provided with a centrally located fastener receiving hole 3 . In the preferred embodiment the top portion 2 of the clip is rectangular in shape having side edges for insertion and retention in the groove of the structural member. In alternative embodiments of the present invention, the top portion 2 may be of any other shape that is suitable such as a circle, oval or biscuit. In the preferred embodiment the fastener receiving hole 3 is located in the center of the top portion 2 overlying the space between the legs 5 . In the preferred embodiment the thickness of the top portion 2 corresponds to the width of the groove 9 of the structural member 8 to enable the insertion and retention of the side edges of the top portion 2 in the groove 9 by way of a friction fit against the top or bottom inner surfaces of the groove as will be hereafter described.
[0022] As shown in FIGS. 1 and 2 , two spaced apart vertical leg members 5 project downwardly from the underside of the top portion 2 on each side of the fastener receiving hole 3 . As can be seen in FIG. 2 the legs 5 are located inwardly from the outer periphery of the clip device 1 to define opposed side edges 11 for insertion into the grooves of adjacent structural members. The vertical leg members 5 have a length equal to the height of the bottom edge portion of the structural member. When one side edge of the top portion of the clip device is inserted into the groove of a structural member, the outer surface of one leg will abut the bottom edge of the structural member as shown in FIG. 4 . Similarly, insertion of the opposite side edge into the groove of an adjacent structural member will result in the other leg coming into contact with the bottom edge of the structural member. In this way the horizontal distance or span between the legs provides uniform spacing between the structural members when installed. In the preferred embodiment the vertical leg members 5 extend parallel to each other and are of uniform shape, thickness and length.
[0023] Use of the clip device 1 to install a decking system is schematically illustrated in FIG. 4 . The system has a plurality of joists 10 (only one is shown), a plurality of structural members 8 (two are shown), a plurality of clip devices 1 (only one is shown). The joists 10 are laid out in a usual regularly spaced apart relationship. The structural members 8 are fastened to the upper surfaces of the joints in a spaced apart side-by-side manner running perpendicular to the joists 10 using the clip devices. Each clip is fastened to the joist by means of a fastening device such as a fastener screw (not shown) passing through the receiving hole 3 which overlies the space between the legs 5 .
[0024] Referring to FIG. 4 , a first structural member 8 is installed to the underlying joist 10 by inserting one side edge 11 into the groove and fastening the clip device 1 to the joist 10 with a fastener 12 . To install an adjacent structural member 8 the opposite side edge 11 of the clip device 1 is inserted into the groove of the adjacent structural member 8 . In each case the clip device 1 is fitted so that each of the vertical legs 5 respectively abuts the bottom edges of the adjacent structural member 8 as shown. The clip device 1 is held in place in the groove by way of a friction fit. Numerous clip devices 1 are thereby similarly inserted and attached at spacing corresponding to the spacing of the underlying joists 10 .
[0025] After installation the structural members 8 may expand and contract widthwise as a result of moisture, humidity and weather thereby exerting a side force on the legs 5 . The spaced apart leg members 5 are compressible inwardly toward each other to accommodate the widthwise expansion of the boards. As the structural members 8 expand, the legs 5 compress inwardly towards each other thereby accommodating the expansion. As the structural members 8 contract, the legs 5 spring back to their original position.
[0026] After installation the structural members 8 may have forces applied along their lengthwise axis. In order to counteract the forces and to resist and prevent lengthwise movement of the structural members 8 with reference to the clip device 1 and each other, the top and/or bottom surface of the top portion 2 of the clip device 1 may be provided with gripping elements 6 to frictionally engage the inner surface of the groove. As shown in FIG. 1 the gripping elements 6 may be comprised of raised parallel ribs extending widthwise across the top surface of the top portion 2 having a vertical height above the surface of the top portion of the clip. The ribs frictionally engage the inner surface of the groove 9 and act to prevent lateral or lengthwise movement of the structural member 8 . In this embodiment, the thickness of the top portion 2 of the clip device 1 including the height of the ribs, must be sized to substantially equal the width of the groove 9 to ensure a friction fit. In alternative embodiments of the present invention the gripping elements 6 may consist of raised protuberances that are suitable to resist the lengthwise movement of the structural members 8 such as, for example, fingers or raised protrusions. The gripping elements 6 may be provided on the bottom surface or the top portion 2 in addition to or instead of the gripping elements 6 provided on the top surface of the top portion 2 to provide additional resistance to movement.
[0027] Further advantages which are inherent to the invention are obvious to one skilled in the art. The embodiments are described herein illustratively and are not meant to limit the scope of the invention as claimed. Variations of the foregoing embodiments will be evident to a person of ordinary skill and are intended by the inventor to be encompassed by the following claims.
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A Π-shaped clip with a top horizontal portion and a pair of integrally formed spaced apart vertical legs underneath. The legs define a spacing distance across their span and are inwardly compressible toward each other in response to a side force. The top portion has raised gripping means for frictional engagement. The clip is inserted into grooves of adjacent structural members secure them to a supporting structure.
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BACKGROUND OF THE INVENTION
[0001] The field of the invention is jewelry, specifically, a bracelet used to remind the wearer of milestones that have been achieved toward a particular goal, and to motivate the wearer to achieve further milestones.
[0002] Typically, major personal goals involve breaking the goal down into a number of discrete sequentially-achieved milestones. Some major personal goals (e.g. conquering addiction “one day at a time”, training for a triathlon) are achieved by marking certain milestones defined by discrete time periods (e.g. days/months/years of sobriety, number of miles trained per week). Since most major personal goals are achieved over a long period of time, it is desirable to have a means of keeping a person motivated because motivation often fluctuates over a long period of time. One of the ways in which a person can maintain their motivation is to wear a tangible item that reminds them of their long term goal and the milestones required to achieve such a goal.
[0003] There are a variety of jewelry items that have been invented to address this problem. For example, the Goal Patrol® bracelet (http://goalpatrol.com), disclosed by Shapiro in US2010/0255451A1, uses separate bracelets, each denoting achievement of a separate milestone, in order to motivate users to achieve their goals. The Pound Puncher™ system used for weight loss uses a plastic token that fits into a plurality of holes in the bracelet, where each hole represents a particular milestone. Another system, disclosed in application Ser. No. 12/384,445 (US 2010/0255451A1), uses a succession of bracelets showing specific symbology to motivate a user toward achieving a goal. However, none of these systems solves the problem with the simplicity reflected in the current invention.
BRIEF SUMMARY OF THE INVENTION
[0004] The current invention is a bracelet comprised of a flexible material such as silicone. The bracelet features a plurality of buttons, with each button representing an individual milestone. As each milestone is achieved, the button in the bracelet corresponding to this milestone is permanently detached from the bracelet. Each of the buttons is cast from the same material as the bracelet itself.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 is a front view of a preferred embodiment of the invention.
[0006] FIG. 2 is a rear view of a preferred embodiment of the invention.
[0007] FIG. 3 is cross-sectional view A-A of FIG. 1 of a preferred embodiment of the invention showing the annular indentations facilitating detachment of the buttons.
DETAILED DESCRIPTION OF THE INVENTION
[0008] As shown in FIGS. 1 and 2 , the invention consists of a bracelet comprised of a flexible material which allows the bracelet to elastically flex when the user puts the bracelet on, obviating the need for a clasping means. As shown in FIG. 1 , bracelet 1 features one or more buttons 2 which are permanently detachable by using pressure commensurate with that generated by an average human pressing relatively firmly with a finger (e.g. 5-20 psi). In order to facilitate detachment of the buttons, there is an annular (in the preferred embodiment) indentation in the bracelet material surrounding the buttons as shown in FIG. 3 , which is a cross section of the bracelet at one of the buttons. Shown in cross section, the silicone material in the preferred embodiment is reduced to a thickness of approximately 0.5-1.5 mm to facilitate easy removal of the buttons.
[0009] The bracelet can be comprised of any one of a variety of suitable elastic materials known to the art, although silicone is used in the preferred embodiment. The bracelet is manufactured using techniques well known to the art, such as injection molding or casting. Although the buttons 2 may be emplaced around the entire circumference of the bracelet, in certain applications, a motivational phrase, symbol, or picture may be applied to the surface of the bracelet, as is shown in FIG. 2 .
[0010] It should be noted that, although the buttons shown are circular in shape, they can be of any shape (e.g. square, star, triangle).
[0011] The bracelet described above provides a tangible reminder to a person intent on achieving a long-term goal. Such a tangible reminder often assists persons in achieving milestones leading to such a goal. One example application would be a bracelet used by persons recovering from addiction. Each button on the bracelet could then represent a day/month/year of sobriety, and the button representing a particular milestone would be removed as each milestone is met. Doing so provides a very visual reminder of what has been achieved, as well as milestones yet to be achieved.
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A motivational bracelet for tracking milestones toward long term goals is comprised of a flexible material and featuring one or more detachable buttons.
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FIELD OF THE DISCLOSURE
The invention relates to electrocoat coating compositions, methods of preparing them, methods of electrodeposition of coatings onto a conductive substrate, and electrodeposited coatings.
BACKGROUND OF THE DISCLOSURE
The statements in this section merely provide background information related to this disclosure and may not constitute prior art.
Industrial coating of metal articles that will be used in corrosive environments may include application of one or more inorganic and organic treatments and coatings. Painting systems (“paint shops”) in automotive assembly plants are large, complex, and expensive. Metal automotive vehicle bodies (the “body-in-white”) and parts, for instance, are given a many-step treatment of cleaning in one or more cleaning baths or spray tanks, application of an aqueous phosphate coating material as a metal pretreatment step in a phosphating bath, then various rinses and additional finishing treatments, such as described in Claffey, U.S. Pat. No. 5,868,820. The phosphating pre-treatment steps are undertaken to improve corrosion resistance of the metal and adhesion of subsequent coatings to the metal. The cleaning and phosphating steps may have 10 or 12 individual treatment stations of spray equipment or dip tanks.
An electrodeposition coating (“electrocoat”) is applied after the pretreatment steps to the metal vehicle body. Electrocoat baths usually comprise an aqueous dispersion or emulsion of a principal film-forming resin (“polymer” and “resin” are used interchangeably in this disclosure), having ionic stabilization in water or a mixture of water and organic cosolvent. In automotive or industrial applications for which durable electrocoat films are desired, the electrocoat compositions are formulated to be curable (thermosetting) compositions. This is usually accomplished by emulsifying with the principal film-forming resin a crosslinking agent that can react with functional groups on the principal resin under appropriate conditions, such as with the application of heat, and so cure the coating. During electrodeposition, coating material containing the ionically-charged resin having a relatively low molecular weight is deposited onto a conductive substrate by submerging the substrate in the electrocoat bath and then applying an electrical potential between the substrate and a pole of opposite charge, for example, a stainless steel electrode. The charged coating material migrates to and deposits on the conductive substrate. The coated substrate is then heated to cure or crosslink the coating.
One of the advantages of electrocoat compositions and processes is that the applied coating composition forms a uniform and contiguous layer over a variety of metallic substrates regardless of shape or configuration. This is especially advantageous when the coating is applied as an anticorrosive coating onto a substrate having an irregular surface, such as a motor vehicle body. The even, continuous coating layer over all portions of the metallic substrate provides maximum anticorrosion effectiveness. The phosphate pre-treatment, however, has up to now been an indispensable step in protecting against corrosion for automotive vehicle bodies. McMurdie et al., U.S. Pat. No. 6,110,341 teaches that hydrocarbyl phosphate and phosphonic acid esters, which may include polyepoxide linking groups, can be incorporated into electrodeposition baths in amounts of up to 500 ppm on total bath weight for improved corrosion protection. Examples including phenylphosphonic acid were reported to have a modest increase in corrosion protection over untreated steel panels.
SUMMARY OF THE DISCLOSURE
We disclose a composition and process for electrodepositing an electrocoat coating on an unphosphated metal substrate (that is, a metal substrate that has not undergone a phosphate pretreatment) in which the electrocoat coating provides excellent corrosion protection. Elimination of the steps and equipment for the phosphating pretreatment process permits a major cost savings in construction of a new paint shop, as well as a simplification and cost savings in operating paint shops now in automotive manufacturing plants.
The process uses an aqueous electrocoat coating composition, also called an electrocoat bath, with a binder comprising a cathodically electrodepositable coating including a vinyl, e.g. acrylic, polymer having at least one phosphorous-containing group
in which X is a hydrogen, a monovalent hydrocarbon group (i.e., hydrocarbyl group), an alkyl group such as an aminoalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or an oxygen atom having a single covalent bond to the phosphorous atom, and each oxygen atom has a covalent bond to a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or the acrylic polymer, with the caveat that at least one oxygen atom has a covalent bond to the acrylic polymer. The alkyl groups may be cycloalkyl groups. The alkyl and aryl groups may be hydrocarbyl groups or may include heteroatoms. For convenience, “polymer” and “resin” are used interchangeably in this disclosure to encompass resin, oligomer, and polymer, and the acrylic polymer having the phosphorous-containing group will be referred to as a phosphorylated acrylic polymer. “Binder” refers to the film-forming components of the coating composition. Typically the binder is thermosetting or curable. The phosphorylated acrylic polymer may itself be electrodepositable, i.e., it may be amine-functional for cathodic electrodeposition or acid-functional for anodic electrodeposition, or the binder may include a further polymer that is electrodepositable. An acrylic polymer is a vinyl polymer prepared by addition polymerization of at least one acrylate or methacrylate monomer, optionally with other vinyl monomers. For convenience, “acrylic” and “vinyl” will be used interchangeably to refer to polymers of vinyl monomers (such as acrylate and mehacylate monomers), as typically at least one acrylate or methacrylate monomer is copolymerized.
In one embodiment, the phosphorylated acrylic polymer comprises a monophosphate ester or monophosphonic acid ester of the acrylic polymer (i.e., one oxygen is covalently bonded to both phosphorous atom and acrylic polymer). In another embodiment, the phosphorylated acrylic polymer comprises a diphosphate ester, triphosphate ester, or diphosphonic acid ester of the acrylic polymer. In other embodiments, the phosphorylated acrylic polymer includes a combination of these esters. The remaining oxygens on the phosphorous atom that are not covalently bound between the polymer and the phosphorous atom may also be esterified with an alkyl group, an aryl group, an alkylaryl group, or an arylalkyl group. In certain embodiments, at least one P—OH group remains unesterified; that is, in these embodiments the phosphorous containing group has at least one P—OH group.
In various embodiments, the phosphorylated acrylic polymer has one phosphorous-containing group or a plurality of phosphorous-containing groups. The phosphorylated acrylic polymer may be prepared using an acrylic polymer with at least one epoxide group or hydroxyl group, or a plurality of such groups, that is reacted with a P—OH group of a phosphorous-containing compound.
In certain embodiments, the phosphorylated acrylic polymer is amine-functional and may be from about 0.01 to about 99% by weight of the total binder in the electrodeposition coating composition. Among these embodiments are those in which the phosphorylated acrylic polymer is from about 1 to about 90% by weight of total binder in the electrodeposition coating composition and those in which the phosphorylated acrylic polymer is from about 5 to about 80% by weight of total binder in the electrodeposition coating composition. In certain embodiments, the binder comprises a crosslinker reactive during cure with the phosphorylated acrylic polymer. In certain embodiments, the binder comprises a second amine-functional resin other than the phosphorylated acrylic polymer. In any of these embodiments, the binder may also comprises a crosslinker that reacts during cure of the electrodeposited coating layer with the phosphorylated acrylic polymer, the second amine-functional resin, or both.
We also disclose a method of coating an electrically conductive substrate, such as a metal automotive vehicle body or part, which comprises placing the electrically conductive substrate into the aqueous electrodeposition coating composition having an electrodepositable binder comprising a phosphorylated acrylic polymer and, using the electrically conductive substrate as one electrode, passing a current through the aqueous electrodeposition coating composition to deposit a coating layer comprising the binder onto the electrically conductive substrate. In certain embodiments of the method, the binder is cathodically electrodepositable and the substrate is a cathode. The deposited coating layer may then be cured to a cured coating layer. Subsequent coating layers may be applied on the (optionally cured) electrodeposited coating layer. For example, the electrodeposited coating layer may be a primer layer and other layers such as an optional spray-applied primer surfacer and a topcoat layer or topcoat layers (e.g., a colored basecoat layer and a clearcoat layer) may be applied over the electrodeposited coating layer. All coating layers may be cured.
In one embodiment of the method, the electrically conductive substrate is unphosphated before it is coated with an electrodeposited coating comprising the phosphorylated acrylic resin; that is, the substrate is free of a phosphate pre-treatment.
In one embodiment of the method, a metal automotive vehicle body is cleaned, and the cleaned metal automotive vehicle body is electrodeposited with an aqueous coating composition comprising an electrodepositable binder comprising a phosphorylated acrylic polymer. Thus, no phosphate pretreatment is used. The binder of the electrocoat coating composition may include a second, amine-functional resin that does not have phosphorous-containing groups, and generally a crosslinker reactive with one or both of the phosphorylated acrylic polymer and the amine-functional resins is included in the coating composition so that the electrodeposited coating layer may be cured.
A coated, electrically conductive substrate comprises an electrically deposited coating layer on the substrate, the electrically deposited coating layer comprising a cured coating formed from a binder comprising a phosphorylated acrylic polymer. In various embodiments, the binder further comprises a crosslinker reactive with the phosphorylated acrylic resin, a second resin in the binder, or both that reacts during cure to form the cured coating.
The phosphorous-containing groups incorporated into the coating composition provide significant improvement in corrosion protection over untreated, particularly unphosphated, metallic substrates such as cold rolled steel, while the acrylic-containing binder allows coatings to be made in a range of colors not possible with an epoxy-based binder system because of the yellow color of most epoxy resins. In addition, an acrylic polymer is more durable when the coating is subjected to outdoor exposure. Further, the phosphorous-containing groups can be easily included in any fraction of monomer units of the acrylic polymer.
“A,” “an,” “the,” “at least one,” and “one or more” are used interchangeably to indicate that at least one of the item is present; a plurality of such items may be present. Other than in the working examples provides at the end of the detailed description, all numerical values of parameters (e.g., of quantities or conditions) in this specification, including the appended claims, are to be understood as being modified in all instances by the term “about” whether or not “about” actually appears before the numerical value. “About” indicates that the stated numerical value allows some slight imprecision (with some approach to exactness in the value; approximately or reasonably close to the value; nearly). If the imprecision provided by “about” is not otherwise understood in the art with this ordinary meaning, then “about” as used herein indicates at least variations that may arise from ordinary methods of measuring and using such parameters. In addition, disclosure of ranges includes disclosure of all values and further divided ranges within the entire range.
Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.
DETAILED DESCRIPTION
The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses.
A metal substrate, which may be unphosphated, is electrocoated with an aqueous electrocoat coating composition having a binder comprising a phosphorylated acrylic polymer. The phosphorylated acrylic polymer either is electrodepositable itself—that is, it has amine or acid functionality—or the binder contains a second polymer that has amine or acid functionality so that the binder is electrodepositable. The electrodeposited coating layer may be cured and may be overcoated with one or more additional coating layers. The phosphorylated acrylic polymer has at least one covalently bonded, phosphorous-containing group having a structure
in which X is a hydrogen, a monovalent hydrocarbon group (i.e., hydrocarbyl group), an alkyl group such as an aminoalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or an oxygen atom having a single covalent bond to the phosphorous atom, and each oxygen atom has a covalent bond to a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or the acrylic polymer, with the caveat that at least one oxygen atom has a covalent bond to the acrylic polymer. In each case, an alkyl group may be a cycloalkyl group and the alkyl or aryl groups may include one or more heteroatoms.
A phosphorylated vinyl or acrylic polymer may be prepared by esterifying a vinyl or acrylic polymer having epoxide or hydroxyl functionality or both with a phosphorous-containing acid or esterifiable derivative, or may be prepared by addition polymerizing a ethylenically unsaturated monomer that has the phosphorous-containing group or has been esterified with the phosphorous-containing acid or acid derivative. Reaction of the phosphorous-containing acid or esterifiable derivative with a hydroxyl group produces an ester linkage, while reaction with an epoxide group produces and ester linkage with a hydroxyl group on a beta carbon.
Nonlimiting, suitable examples of addition polymerizable monomers that may be reacted with the phosphorous-containing acid or derivative or that can be copolymerized to provide a hydroxyl or epoxide group on the acrylic polymer for reaction with the phosphorous-containing acid or derivative include, without limitation, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, allyl alcohol, glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether; these may be used in combinations. If hydroxyl or epoxide groups are also to be used as crosslinkable functionality during cure of the coating, the amount of hydroxyl or epoxide groups incorporated is increased over what is needed for reaction with the phosphorous-containing acid or esterifiable derivative to provide the desired residual amount of the hydroxyl or epoxide groups for crosslinking during cure.
The addition polymerizable monomer bearing the hydroxyl, epoxide, or phosphorous-containing group may be copolymerized with other addition polymerizable monomers in forming the acrylic polymer. Nonlimiting examples of suitable comonomers include α,β-ethylenically unsaturated monocarboxylic acids containing 3 to 5 carbon atoms and ethylenically unsaturated dicarboxylic acid and anhydrides; esters, nitriles, or amides of α,β-ethylenically unsaturated monocarboxylic acids containing 3 to 5 carbon atoms and ethylenically unsaturated dicarboxylic acid and anhydrides; vinyl esters, vinyl ethers, vinyl ketones, vinyl amides, and vinyl compounds of aromatics and heterocycles. Representative examples include acrylic and methacrylic acids, amides, and aminoalkyl amides; acrylonitrile and methacrylonitriles; esters of acrylic and methacrylic acid, including those of saturated aliphatic and cycloaliphatic alcohols containing 1 to 20 carbon atoms such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, amyl acrylate, amyl methacrylate, isoamyl acrylate, isoamyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, decyl acrylate, decyl methacrylate, isodecyl acrylate, isodecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, substituted cyclohexyl acrylates and methacrylates, 3,5,5-trimethylhexyl acrylate, 3,5,5-trimethylhexyl methacrylate; dimethylaminoethyl, tert-butyl amino, tetrahydrofurfuryl, and isobornyl acrylates and methacrylates; the corresponding esters of maleic, fumaric, crotonic, isocrotonic, vinylacetic, and itaconic acids, and the like, such as maleic acid dimethyl ester and maleic acid monohexyl ester; vinyl monomers such as vinyl acetate, vinyl propionate, vinyl ethyl ether, and vinyl ethyl ketone, styrene, α-methyl styrene, vinyl toluene, 2-vinyl pyrrolidone, t-butyl styrene, and the like. Other useful polymerizable co-monomers include, for example, alkoxyethyl acrylates and methacrylates, acryloxy acrylates and methacrylates, and compounds such as acrylonitrile, methacrylonitrile, acrolein, and methacrolein. Combinations of these are usually employed.
Acrylic polymers may be prepared by using conventional techniques, such as free radical polymerization, cationic polymerization, or anionic polymerization, in, for example, a batch, semi-batch, or continuous feed process. For instance, the polymerization may be carried out by heating the ethylenically unsaturated monomers in bulk or in solution in the presence of a free radical source, such as an organic peroxide or azo compound and, optionally, a chain transfer agent, in a batch or continuous feed reactor. Alternatively, the monomers and initiator(s) may be fed into the heated reactor at a controlled rate in a semi-batch process.
Typical free radical sources are organic peroxides such as dialkyl peroxides, peroxyesters, peroxydicarbonates, diacyl peroxides, hydroperoxides, and peroxyketals; and azo compounds such as 2,2′-azobis(2-methylbutanenitrile) and 1,1′-azobis(cyclohexanecarbonitrile). Typical chain transfer agents are mercaptans such as octyl mercaptan, n- or tert-dodecyl mercaptan, thiosalicylic acid, mercaptoacetic acid, and mercaptoethanol; halogenated compounds, and dimeric alpha-methyl styrene. The free radical polymerization is usually carried out at temperatures from about 20° C. to about 250° C., preferably from 90° C. to 170° C. The reaction is carried out according to conventional methods to produce a vinyl copolymer.
Suitable phosphorous containing acid derivatives that may be reacted with an epoxide- or hydroxyl-functional acrylic polymer or monomer include esterifiable esters and anhydrides of phosphorous-containing acids. Among suitable examples. are those —P(OR) 2 ═O group-containing acids or acid derivatives having at least one R that is a hydrogen atom or a lower alkyl group (up to four carbon atoms, particularly methyl, ethyl, propyl, isopropyl, and tert-butyl) than can be transesterified, such as phosphoric acid, a mono- or diester of phosphoric acid, hypophosphoric acid, a monoester of hypophosphoric acid, alkyl- or arylphosphonic acid, a monoester of alkyl- or arylphosphonic acid, and combinations of these. Phosphoric acid or a source of phosphoric acid that used in the reaction may be nonaqueous phosphoric acid, 85% in water, a more dilute aqueous phosphoric acid, pyrophosphoric acid, or polyphosphoric acid. Other suitable phosphoric acid sources are described in Campbell et al., U.S. Pat. No. 4,397,970, incorporated herein by reference. The acrylic polymer has at least one epoxide or hydroxyl group for reaction with the phosphorous-containing acid or acid derivative.
The phosphorous-containing acid or acid derivative may be reacted with a polymerizable monomer before polymerization of the acrylic polymer or with the acrylic polymer during or after polymerization. The reaction with the acid or acid derivative with polymer or monomer may be carried out at a temperature of from about 50° C. to about 150° C. in solvent such as any of those already mentioned, or neat. If carried out before polymerization (that is, with an addition polymerizable, ethylenically unsaturated monomer), it is advisable to use a small amount of polymerization inhibitor (e.g., hydroquinone or methylhydroquinone) to preserve the addition polymerizable unsaturated group. Suitable solvents include, without limitation, inert organic solvent such as a ketone, including methyl isobutyl ketone and methyl amyl ketone, aromatic solvents such as toluene, xylene, Aromatic 100, and Aromatic 150, and esters, such as butyl acetate, n-propyl acetate, hexyl acetate.
The phosphorylated acrylic polymer may include monophosphonic acid esters, diphosphonic acid esters, monophosphate ester, diphosphate esters, and triphosphate esters of the acrylic polymer, as well as combinations of these. In addition, the phosphorylated acrylic polymer may have one or a plurality of the phosphorous-containing ester groups. The extent of esterification by the phosphorous-containing acid or acid derivative and the number of phosphorous-containing ester groups incorporated into the resin may be controlled, inter alia, by the relative equivalents of the reactants. In one example, from about 1 to about 3 equivalents of vinyl or acrylic polymer (based on epoxide and/or hydroxyl groups) is reacted with each equivalent of phosphoric acid or phosphoric acid derivative. In another example, from about 1 to about 2 equivalents of acrylic polymer (based on epoxide and hydroxyl groups) is reacted with each equivalent of phosphonic acid or phosphonic acid derivative. The equivalents of the polymer reactive groups may also be in excess of the equivalents of acid or acid derivative. The polymer and phosphoric or phosphonic acid or acid derivative may be mixed together and allowed to react until a desired extent of reaction is obtained. In some embodiments, the acrylic or vinyl polymer has from about 0.01 to about 1 milliequivalents phosphorous-containing groups per gram; in some embodiments, the acrylic or vinyl polymer has from about 0.01 to about 0.1 milliequivalents phosphorous-containing groups per gram.
Other reactants that may be used in the phosphorylation reaction in addition to the acrylic polymer and phosphorous-containing acid or acid derivative may include alkyl or aromatic alcohols such as n-butanol, isopropanol, and n-propanol; glycol ethers such as ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and propylene glycol monopropyl ether; alkyl or aromatic amines such as dimethylethanolamine, diethanolamine, dipropanolamine, diisopropanolamine, dibutanolamine, diisobutanolamine, diglycolamine, methylethanolamine, dimethylaminopropylamine; water; and combinations of these. Such reactants can also be used to react with excess oxirane or hydroxyl groups after the reaction of the acrylic polymer with the acid or acid derivative. Similarly, such other reactants may be included when a polymerizable monomer having an epoxide or hydroxyl group is reacted with the phosphorous-containing acid or acid derivative before polymerization of the acrylic polymer.
The acrylic resins may be made anodically electrodepositable by incorporation of acid functionality, for example by polymerization of acid-containing monomers such as acrylic acid, methacrylic acid, unsaturated dicarboxylic acids or cyclic anhydrides of these. The acrylic resins may be made cathodically electrodepositable by incorporation of amine functionality, for example by polymerization of amino-containing monomers such as N,N′-dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate. N,N′-dimethylaminoethyl acrylate, tert-butylaminoethyl acrylate. 2-vinylpyridine, 4-vinylpyridine, vinylpyrrolidine or other such amino monomers. Alternatively, epoxide groups may be incorporated by including an epoxide-functional monomer in the polymerization reaction (or an excess over that required for reaction with the phosphorous-containing acid or reactive derivative) and then reacted with an amine such as a secondary amine. If the epoxide groups area also used to introduce the phosphorous-containing group onto the acrylic polymer, a sufficient amount of epoxide groups are incorporated for both purposes. The amine functionality may be imparted to the acrylic polymer with epoxide functionality in one of two ways. In a first way, an amine having at least one active hydrogen reactive with an epoxide group is included as a reactant in the reaction of the epoxide-functional resin and phosphorous-containing acid or source of phosphorous-containing acid. In a second way, the phosphorylated acrylic polymer is formed as an epoxide-functional product that is then further reacted with an amine having at least one active hydrogen reactive with an epoxide group. Examples of suitable amine compounds include, without limitation, dimethylaminopropylamine, N,N-diethylaminopropylamine, dimethylaminoethylamine, N-aminoethylpiperazine, aminopropylmorpholine, tetramethyldipropylenetriamine, methylamine, ethylamine, dimethylamine, dibutylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, dimethylaminobutylamine, diethylaminopropylamine, diethylaminobutylamine, dipropylamine, methylbutylamine, alkanolamines such as methylethanolamine, aminoethylethanolamine, aminopropylmonomethylethanolamine, and diethanolamine, diketimine (a reaction product of 1 mole diethylenetriamine and 2 moles methyl isobutyl ketone), and polyoxyalkylene amines.
The monomer(s) bearing the epoxide group, hydroxyl group, and/or phosphorous-containing group and the monomer bearing the group for salting (amine for a cationic group or acid or anhydride for anionic group) may be polymerized with one or more other ethylenically unsaturated monomers, such as those already mentioned.
The phosphorylated acrylic polymer is used to prepare an electrocoat coating composition (also known as an electrocoat bath). In general, a binder is prepared comprising the phosphorylated acrylic polymer, then the binder is dispersed in an aqueous medium by salting amine groups present in the binder with an acid to give a cathodically depositable electrocoat composition or by salting acid groups present in the binder with an amine to give an anodically-depositable electrocoat composition and combining the salted binder with an aqueous medium.
In certain embodiments, the binder in the electrodeposition coating composition comprises from about 0.01 to about 99% by weight of phosphorylated acrylic polymer. The binder in the electrodeposition coating composition may comprise from about 0.01 to about 99% by weight of phosphorylated acrylic polymer, 1 to about 90% by weight of phosphorylated acrylic polymer, or from about 5 to about 80% by weight of phosphorylated acrylic polymer.
If the phosphorylated acrylic polymer does not have amine or acid functionality, then the binder comprises a second polymer than is amine-functional or acid-functional that makes the binder electrodepositable. The second resin may be made an acrylic resin that is made amine-functional as described above by incorporation of amino-containing monomers, such as N,N′-dimethylaminoethyl methacrylate tert-butylaminoethyl methacrylate. N,N′-dimethylaminoethyl acrylate tert-butylaminoethyl acrylate. 2-vinylpyridine, 4-vinylpyridine, vinylpyrrolidine or other such amino monomers or by reaction of epoxide groups with amines as previously described, or that is made acid-functional by incorporation of a polymerizable acid such as those already mentioned. The polymerization may also include a hydroxyl-functional monomer to provide crosslinkable functional groups. Useful hydroxyl-functional ethylenically unsaturated monomers include, without limitation, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, the reaction product of methacrylic acid with styrene oxide, and so on. Preferred hydroxyl monomers are methacrylic or acrylic acid esters in which the hydroxyl-bearing alcohol portion of the compound is a linear or branched hydroxy alkyl moiety having from 1 to about 8 carbon atoms.
The monomer bearing the hydroxyl group and the monomer bearing the amine or epoxide group or the acid group may be polymerized with any of the other ethylenically unsaturated monomers already mentioned in connection with the phosphorylated acrylic polymer. Combinations of comonomers are usually employed.
The binder may also comprise a crosslinker that reacts with the amine-functional resin other than the phosphorylated resin during curing of a coating layer formed on a substrate, or the binder may also comprise a crosslinker that reacts with both the amine-functional resin other than the phosphorylated resin and the phosphorylated resin during curing of a coating layer formed on a substrate. Suitable examples of crosslinking agents, include, without limitation, blocked polyisocyanates and aminoplast resins. Examples of aromatic, aliphatic or cycloaliphatic polyisocyanates include diphenylmethane-4,4′-diisocyanate (MDI), 2,4- or 2,6-toluene diisocyanate (TDI), p-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, mixtures of phenylmethane-4,4′-diisocyanate, polymethylene polyphenylisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, dicyclohexylmethane 2,4′-diisocyanate, 1,3-bis(iso-cyanatomethyl)cyclohexane, diisocyanates derived from dimer fatty acids, as sold under the commercial designation DDI 1410 by Henkel, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,7-diisocyanato-4-isocyanato-methylheptane or 1-isocyanato-2-(3-isocyanatopropyl)-cyclohexane, and higher polyisocyanates such as triphenylmethane-4,4′,4″-triisocyanate, or mixtures of these polyisocyanates. Suitable polyisocyanates also include polyisocyanates derived from these that containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, or uretdione groups. Polyisocyanates containing urethane groups, for example, are obtained by reacting some of the isocyanate groups with polyols, such as trimethylolpropane, neopentyl glycol, and glycerol, for example. The isocyanate groups are reacted with a blocking agent. Examples of suitable blocking agents include phenol, cresol, xylenol, epsilon-caprolactam, delta-valerolactam, gamma-butyrolactam, diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate, alcohols such as methanol, ethanol, isopropanol, propanol, isobutanol, tert-butanol, butanol, glycol monoethers such as ethylene or propylene glycol monoethers, acid amides (e.g. acetanilide), imides (e.g. succinimide), amines (e.g. diphenylamine), imidazole, urea, ethylene urea, 2-oxazolidone, ethylene imine, oximes (e.g. methylethyl ketoxime), and the like.
As understood by those skilled in the art, an aminoplast resin is formed by the reaction product of formaldehyde and amine where the preferred amine is a urea or a melamine. Although urea and melamine are the preferred amines, other amines such as triazines, triazoles, diazines, guanidines, or guanamines may also be used to prepare the aminoplast resins. Furthermore, although formaldehyde is preferred for forming the aminoplast resin, other aldehydes, such as acetaldehyde, crotonaldehyde, and benzaldehyde, may also be used. Nonlimiting examples of suitable aminoplast resins include monomeric or polymeric melamine-formaldehyde resins, including melamine resins that are partially or fully alkylated using alcohols that preferably have one to six, more preferably one to four, carbon atoms, such as hexamethoxy methylated melamine; urea-formaldehyde resins including methylol ureas and siloxy ureas such as butylated urea formaldehyde resin, alkylated benzoguanimines, guanyl ureas, guanidines, biguanidines, polyguanidines, and the like.
Optionally, plasticizer or solvents or both can be added to the electrocoat coating composition. Nonlimiting examples of coalescing solvents include alcohols, glycol ethers, polyols, and ketones. Specific coalescing solvents include monobutyl and monohexyl ethers of ethylene glycol, phenyl ether of propylene glycol, monoalkyl ethers of ethylene glycol such as the monomethyl, monoethyl, monopropyl, and monobutyl ethers of ethylene glycol or propylene glycol; dialkyl ethers of ethylene glycol or propylene glycol such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; butyl carbitol; diacetone alcohol. Nonlimiting examples of plasticizers include ethylene or propylene oxide adducts of nonyl phenols, bisphenol A, cresol, or other such materials, or polyglycols based on ethylene oxide and/or propylene oxide. The amount of coalescing solvent is not critical and is generally between about 0 to 15 percent by weight, preferably about 0.5 to 5 percent by weight based on total weight of the resin solids. Plasticizers can be used at levels of up to 15 percent by weight resin solids.
An amine-functional binder is emulsified in water in the presence of an acid or an acid-functional binder is emulsified in water in the presence of a base. Nonlimiting examples of suitable acids include phosphoric acid, phosphonic acid, propionic acid, formic acid, acetic acid, lactic acid, or citric acid. Nonlimiting examples of suitable bases include ammonia and amines. The salting acid or base may be blended with the binder, mixed with the water, or both, before the binder is added to the water. The acid or base is used in an amount sufficient to neutralize enough of the amine or acid groups to impart water-dispersibility to the binder. The amine or acid groups may be fully neutralized; however, partial neutralization is usually sufficient to impart the required water-dispersibility. By saying that the resin is at least partially neutralized, we mean that at least one of the saltable groups of the binder is neutralized, and up to all of such groups may be neutralized. The degree of neutralization that is required to afford the requisite water-dispersibility for a particular binder will depend upon its composition, molecular weight of the resins, weight percent of saltable resin in the binder, and other such factors and can readily be determined by one of ordinary skill in the art through straightforward experimentation.
The binder emulsion is then used in preparing an electrocoat coating composition (or bath). The electrocoat bath may contain no pigment so as to produce a colorless or clear electrodeposited coating layer, but the electrocoat bath usually includes one or more pigments, generally added as part of a pigment paste, and may contain any further desired materials such as coalescing aids, antifoaming aids, and other additives that may be added before or after emulsifying the binder. The pigments used may be inorganic pigments, including metal oxides, chromates, molybdates, phosphates, and silicates. Examples of inorganic pigments and fillers that could be employed are titanium dioxide, barium sulfate, carbon black, ocher, sienna, umber, hematite, limonite, red iron oxide, transparent red iron oxide, black iron oxide, brown iron oxide, chromium oxide green, strontium chromate, zinc phosphate, silica, calcium carbonate, talc, barytes, ferric ammonium ferrocyanide (Prussian blue), ultramarine, lead chromate, lead molybdate, aluminum silicate, precipitated barium sulfate, aluminum phosphomolybdate, and mica flake pigments. Organic pigments may also be used. Examples of useful organic pigments are metallized and non-metallized azo reds, quinacridone reds and violets, perylene reds, copper phthalocyanine blues and greens, carbazole violet, monoarylide and diarylide yellows, benzimidazolone yellows, tolyl orange, naphthol orange, and the like. The pigments may be dispersed using a grind resin or a pigment dispersant. The pigment-to-resin weight ratio in the electrocoat bath can be important and should be preferably less than 50:100, more preferably less than 40:100, and usually about 10 to 30:100. Higher pigment-to-resin solids weight ratios have been found to adversely affect coalescence and flow. Usually, the pigment is 10-40 percent by weight of the nonvolatile material in the bath. Preferably, the pigment is 15 to 30 percent by weight of the nonvolatile material in the bath. Any of the pigments and fillers generally used in electrocoat primers may be included.
The electrodeposition coating compositions can contain optional ingredients such as dyes, flow control agents, plasticizers, catalysts, wetting agents, surfactants, UV absorbers, HALS compounds, antioxidants, defoamers and so forth. Examples of surfactants and wetting agents include alkyl imidazolines such as those available from Ciba-Geigy Industrial Chemicals as AMINE C® acetylenic alcohols such as those available from Air Products and Chemicals under the tradename SURFYNOL®. Surfactants and wetting agents, when present, typically amount to up to 2 percent by weight resin solids.
Curing catalysts such as tin catalysts can be used in the coating composition. Typical examples are without limitation, tin and bismuth compounds including dibutyltin dilaurate, dibutyltin oxide, and bismuth octoate. When used, catalysts are typically present in amounts of about 0.05 to 2 percent by weight tin based on weight of total resin solids.
The electrocoat coating composition is electrodeposited onto a metallic substrate and then cured to form a coated article. The electrodeposition of the coating preparations according to the invention may be carried out by processes known to those skilled in the art. The electrodeposition coating composition may be applied on any conductive substrate, such as steel, copper, aluminum, or other metals or metal alloys, preferably to a dry film thickness of 10 to 35 μm. In one embodiment of the method, the electrically conductive substrate is unphosphated; that is, it is free of a phosphate pre-treatment The article coated with the composition of the invention may be a metallic automotive part or body. A method of coating an electrically conductive substrate, such as a metal automotive vehicle body or part, comprises placing an electrically conductive substrate, cleaned but preferably not given a phosphate pre-treatment, into the electrocoat coating composition and, using the electrically conductive substrate as the cathode, passing a current through the electrocoat coating composition causing a coating layer to deposit onto the electrically conductive substrate. After application, the coated article is removed from the bath and rinsed with deionized water. The coating may be cured under appropriate conditions, for example by baking at from about 275° F. to about 375° F. for between about 15 and about 60 minutes.
An automotive vehicle body may be electrocoated. The automotive vehicle body is cleaned, and the cleaned metal automotive vehicle body is electrocoated with an aqueous electrodeposition coating composition comprising the phosphorylated resin.
One or more additional coating layers, such as a spray-applied primer-surfacer, single topcoat layer, or composite color coat (basecoat) and clearcoat layer, may be applied over the electrocoat layer. A single layer topcoat is also referred to as a topcoat enamel. In the automotive industry, the topcoat is typically a basecoat that is overcoated with a clearcoat layer. A primer surfacer and the topcoat enamel or basecoat and clearcoat composite topcoat may be waterborne, solventborne, or a powder coating, which may be a dry powder or an aqueous powder slurry.
The composite coating of the invention may have, as one layer, a primer coating layer, which may also be termed a primer-surfacer or filler coating layer. The primer coating layer can be formed from a solventborne composition, waterborne composition, or powder composition, including powder slurry composition. The primer composition preferably has a binder that is thermosetting, although thermoplastic binders are also known. Suitable thermosetting binders may have self-crosslinking polymers or resins, or may include a crosslinker reactive with a polymer or resin in the binder. Nonlimiting examples of suitable binder polymers or resins include acrylics, polyesters, and polyurethanes. Such polymers or resins may include as functional groups hydroxyl groups, carboxyl groups, anhydride groups, epoxide groups, carbamate groups, amine groups, and so on. Among suitable crosslinkers reactive with such groups are aminoplast resins (which are reactive with hydroxyl, carboxyl, carbamate, and amine groups), polyisocyanates, including blocked polyisocyanates (which are reactive with hydroxyl groups and amine groups), polyepoxides (which are reactive with carboxyl, anhydride, hydroxyl, and amine groups), and polyacids and polyamines (which are reactive with epoxide groups). Examples of suitable primer compositions are disclosed, for example, in U.S. Pat. Nos. 7,338,989; 7,297,742; 6,916,877; 6,887,526; 6,727,316; 6,437,036; 6,413,642; 6,210,758; 6,099,899; 5,888,655; 5,866,259; 5,552,487; 5,536,785; 4,882,003; and 4,190,569, each assigned to BASF and each incorporated herein by reference.
The primer coating composition applied over the electrocoat primer may then be cured to form a primer coating layer. The electrocoat primer may be cured at the same time as the primer coating layer in a process known as “wet-on-wet” coating.
A topcoat composition may be applied over the electrocoat layer or primer coating layer and, preferably, cured to form a topcoat layer. In a preferred embodiment, the electrocoat layer or primer layer is coated with a topcoat applied as a color-plus-clear (basecoat-clearcoat) topcoat. In a basecoat-clearcoat topcoat, an underlayer of a pigmented coating, the basecoat, is covered with an outer layer of a transparent coating, the clearcoat. Basecoat-clearcoat topcoats provide an attractive smooth and glossy finish and generally improved performance.
Crosslinking compositions are preferred as the topcoat layer or layers. Coatings of this type are well-known in the art and include waterborne compositions, solventborne compositions, and powder and powder slurry compositions. Polymers known in the art to be useful in basecoat and clearcoat compositions include, without limitation, acrylics, vinyls, polyurethanes, polycarbonates, polyesters, alkyds, and polysiloxanes. Acrylics and polyurethanes are among preferred polymers for topcoat binders. Thermoset basecoat and clearcoat compositions are also preferred, and, to that end, preferred polymers comprise one or more kinds of crosslinkable functional groups, such as carbamate, hydroxy, isocyanate, amine, epoxy, acrylate, vinyl, silane, acetoacetate, and so on. The polymer may be self-crosslinking, or, preferably, the composition may include a crosslinking agent such as a polyisocyanate or an aminoplast resin. Examples of suitable topcoat compositions are disclosed, for example, in U.S. Pat. Nos. 7,375,174; 7,342,071; 7,297,749; 7,261,926; 7,226,971; 7,160,973; 7,151,133; 7,060,357; 7,045,588; 7,041,729; 6,995,208; 6,927,271; 6,914,096; 6,900,270; 6,818,303; 6,812,300; 6,780,909; 6,737,468; 6,652,919; 6,583,212; 6,462,144; 6,337,139; 6,165,618; 6,129,989; 6,001,424; 5,981,080; 5,855,964; 5,629,374; 5,601,879; 5,508,349; 5,502,101; 5,494,970; 5,281,443; and, each assigned to BASF and each incorporated herein by reference.
The further coating layers can be applied to the electrocoat coating layer according to any of a number of techniques well-known in the art. These include, for example, spray coating, dip coating, roll coating, curtain coating, and the like. For automotive applications, the further coating layer or layers are preferably applied by spray coating, particularly electrostatic spray methods. Coating layers of one mil or more are usually applied in two or more coats (passes), separated by a time sufficient to allow some of the solvent or aqueous medium to evaporate, or “flash,” from the applied layer. The flash may be at ambient or elevated temperatures, for example, the flash may use radiant heat. The coats as applied can be from 0.5 mil up to 3 mils dry, and a sufficient number of coats are applied to yield the desired final coating thickness.
A primer layer may be cured before the topcoat is applied. The cured primer layer may be from about 0.5 mil to about 2 mils thick, preferably from about 0.8 mils to about 1.2 mils thick.
Color-plus-clear topcoats are usually applied wet-on-wet. The compositions are applied in coats separated by a flash, as described above, with a flash also between the last coat of the color composition and the first coat the clear. The two coating layers are then cured simultaneously. Preferably, the cured basecoat layer is 0.5 to 1.5 mils thick, and the cured clear coat layer is 1 to 3 mils, more preferably 1.6 to 2.2 mils, thick.
Alternatively the primer layer and the topcoat can be applied “wet-on-wet.” For example, the primer composition can be applied, then the applied layer flashed; then the topcoat can be applied and flashed; then the primer and the topcoat can be cured at the same time. Again, the topcoat can include a basecoat layer and a clearcoat layer applied wet-on-wet. The primer layer can also be applied to an uncured electrocoat coating layer, and all layers cured together.
The coating compositions described are preferably cured with heat. Curing temperatures are preferably from about 70° C. to about 180° C., and particularly preferably from about 170° F. to about 200° F. for a topcoat or primer composition including an unblocked acid catalyst, or from about 240° F. to about 275° F. for a topcoat or primer composition including a blocked acid catalyst. Typical curing times at these temperatures range from 15 to 60 minutes, and preferably the temperature is chosen to allow a cure time of from about 15 to about 30 minutes. In a preferred embodiment, the coated article is an automotive body or part.
The invention is further described in the following example. The example is merely illustrative and does not in any way limit the scope of the invention as described and claimed. All parts are parts by weight unless otherwise noted.
EXAMPLES
Preparation A. Phosphorylated Acrylic Polymer
A reactor equipped with a reflux condenser and monomer and initiator feed lines is charged with 5.52 parts by weight of toluene. The toluene is heated to reflux. Then simultaneously and uniformly, a monomer mixture (2.10 parts by weight glycidyl methacrylate, 5.32 parts by weight 2-hydroxyethyl methacrylate, 3.28 parts by weight methyl methacrylate, 0.10 parts by weight toluene, 5.72 parts by weight styrene, and 4.77 parts by weight butyl methacrylate) and an initiator mixture (1.045 parts by weight Vazo® 67 and 1.369 parts by weight toluene) are added to the reactor over 3 hours. The temperature is maintained at reflux for an additional 45 minutes after the additions are completed. Then, an initiator mixture (0.211 parts by weight Vazo® 67 and 0.276 parts by weight toluene) is added over 30 minutes and reflux is then maintained for an additional 1.5 hours. The reaction mixture is cooled to about 50° C., then phosphoric acid (75% aqueous) (0.42 parts by weight), butanol (0.18 parts by weight), are added and the reaction mixture is held at reflux for an additional four hours. Then, deionized water is added (0.23 parts by weight) and the reaction temperature is held for an additional three hours. Next, 0.75 parts by weight of methyl ethanol amine and 0.7 parts by weight propylene glycol phenyl ether are added to the reaction mixture, which is allowed to exotherm. The temperature is then held at about 95° C. for two hours, after which 0.74 parts by weight Tetronic® 901 (available from BASF Corporation) and 9.33 parts by weight of an isocyanurate of isophorone diisocyanate blocked with methyl ethyl ketoxime (70% nonvolatile in methyl isobutyl ketone) are added to the reaction product. Finally, 0.7 parts by weight lactic acid and 1.0 parts by weight of deionized water are added and stirred well, followed by an additional and 65.7 parts by weight of deionized water added in portions over two hours.
Preparation B: Grinding Resin Solution Having Tertiary Ammonium Groups
In accordance with EP 0 505 445 B1, an aqueous-organic grinding resin solution is prepared by reacting, in the first stage, 2598 parts of bisphenol A diglycidyl ether (epoxy equivalent weight (EEW) 188 g/eq), 787 parts of bisphenol A, 603 parts of dodecylphenol, and 206 parts of butyl glycol in a stainless steel reaction vessel in the presence of 4 parts of triphenylphosphine at 130° C. until an EEW (epoxy equivalent weight) of 865 g/eq is reached. In the course of cooling, the batch is diluted with 849 parts of butyl glycol and 1534 parts of D.E.R® 732 (polypropylene glycol diglycidyl ether, DOW Chemical, USA) and is reacted further at 90° C. with 266 parts of 2,2′-aminoethoxyethanol and 212 parts of N,N-dimethylaminopropylamine. After 2 hours, the viscosity of the resin solution is constant (5.3 dPas; 40% in SOLVENON® PM (methoxypropanol, BASF/Germany); cone and plate viscometer at 23° C.). It is diluted with 1512 parts of butyl glycol and the base groups are partly neutralized with 201 parts of glacial acetic acid, and the product is diluted further with 1228 parts of deionized water and discharged. This gives a 60% strength aqueous-organic resin solution whose 10% dilution has a pH of 6.0. The resin solution is used in direct form for paste preparation.
Preparation C: Pigment Paste
A premix is first formed from 125 parts of water and 594 parts of the grinding resin of Preparation B. Then 7 parts of acetic acid, 9 parts of Tetronic® 901, 8 parts of carbon black, 547 parts of titanium dioxide TI-PURE® R 900 (DuPont, USA), 44 parts of di-n-butyl tin oxide, 47 parts of bismuth subsalicylate, and 120 parts of ASP200 clay (Langer & Co./Germany) are added. The mixture is predispersed for 30 minutes under a high-speed dissolver stirrer. The mixture is subsequently dispersed in a small laboratory mill (Motor Mini Mill, Eiger Engineering Ltd, Great Britain) until it measures a Hegmann fineness of less than or equal to 12 μm and is adjusted to solids content with additional water. The obtained pigment paste has solids content: 67% by weight (1 hour at 110° C.).
Example 1
A bath was prepared by combining 1096.1 parts Preparation A, 147.3 parts preparation C, and 1256.6 parts deionized water. The water and Preparation A resin emulsion are combined in a container with constant stirring, and Preparation C is added with stirring. The bath solid contents are about 19% by weight.
Example 1 is coated onto both phosphated and bare cold rolled steel 4-inch-by-6-inch test panels at about 225 volts in the Example 1 bath at bath temperatures from 88-98° F. (31-36.7° C.) for 2.2 minutes and the coated panels are baked for 28 minutes at 350° F. (177° C.). The deposited, cured coating layer has a filmbuild of about 0.8 mil (20 μm).
The description is merely exemplary in nature and, thus, variations that do not depart from the gist of the disclosure are a part of the invention. Variations are not to be regarded as a departure from the spirit and scope of the disclosure.
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A coating composition, such as an electrodepositable electrocoat primer coating composition, comprises a phosphorylated acrylic polymer, The coating provides excellent corrosion protection even without a conventional phosphate pretreatment.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims the priority of Chinese patent applications CN201410168805.7, CN201410169225.X, CN201410168779.8, CN201410168730.2, CN201410168798.0, and CN201410168579.2, the entirety of which is incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to the technical field of olefin polymerization, and in particular, to a catalyst component for propene polymerization. The present invention further relates to a preparation method of said catalyst component, and a catalyst containing said catalyst component.
TECHNICAL BACKGROUND
[0003] Generally, catalysts used for olefin polymerization can be classified into three categories: traditional Ziegler-Natta catalyst, metallocene catalyst, and non-metallocene catalyst. For traditional propene polymerization Ziegler-Nattacatalyst, titanium catalysts used for propene polymerization mainly use magnesium, titanium, halogen, and electron donor as basic components, wherein electron donor compounds are indispensible elements of catalyst components. With the development of electron donor compounds in catalysts, olefin polymerization catalysts are also constantly undated, and the development thereof experiences the 1 st generation of TiCl 3 AlCl 3 /AlEt 2 Cl system, the 2 nd generation of TiCl 3 /AlEt 2 Cl system, the 3 rd generation of TiCl 4 .ED.MgCl 2 /AlR 3 .ED system using magnesium chloride as carriers, monoester or aromatic diester as internal electron donor, and silane as external electron donor, and the newly developed catalyst system using diether compounds and diester compounds as internal electron donors. The activity of catalysts for catalytic polymerization reaction and the isotacticity of the obtained polymers are greatly improved. Till now, many internal electron donor components have been disclosed, these components including, for example, monocarboxylic esters or multiple carboxylic esters, acid anhydrides, ketone, monoethers or multiple ethers, alcohols, amines, and derivatives thereof, and so on, wherein commonly used ones are aromatic dicarboxylic esters such as di-n-butyl phthalate or di-n-butyl diisobutyl ester, and so on. Reference can be made to U.S. Pat. No. 4,784,983, U.S. Pat. No. 4,971,937 and European patent EP0728769 disclose components of catalysts used for olefin polymerization, wherein 1,3-diether compounds having two ether groups are used as electron donors, such compounds including, for example, 2-isopropyl-2-isopentyl-1,3-dimethoxy propane, 2,2-diisobutyl-1,3-dimethoxy propane, and 9,9-di(methoxymethyl) fluorene, etc. Later, aliphatic dicarboxylic ester compounds, such as succinate, malonic ester, glutarate, and so on, are disclosed (see WO98/56830, WO98/56834, WO01/57099, WO01/63231, and WO00/55215). However, catalysts prepared with existing internal electron donor compounds generally have defects such as rapid decrease of activity. Besides, taking diether catalysts as an example, diether catalysts have a high activity, and can obtain a polymer with high isotacticity without external electron donors, and have a good hydrogen response, but the molecular weight distribution thereof is very narrow, and the activity thereof decreases fast; while diester catalysts can obtain a polymer with relatively wide molecular weight distribution and rigid-tough balance, the hydrogen response thereof is not that good.
[0004] The present invention aims to provide a new catalyst component and catalyst, wherein the catalyst has a high activity and high long-term stability, and can widen the molecular weight distribution of the obtained polymer, and can enable the obtained polymer to have a high melt index and isotacticity. The obtained polymer has a broad application prospect.
SUMMARY OF THE INVENTION
[0005] Aiming at the deficiencies of the prior art, the present invention provides a catalyst component for propene polymerization, preparation method thereof and a catalyst containing the same. When used for propene polymerization, the catalyst provided by the present invention has a higher activity, orientation ability, good hydrogen response, and high stability (i.e. the activity of the catalyst decreases slowly). The obtained polymer has not only a wider molecular weight distribution, but also a high melt index and isotacticity.
[0006] According to one aspect of the present invention, provided is a catalyst component for propene polymerization, comprising titanium, magnesium, halogen and internal electron donor A, said internal electron donor A being at least one selected from compounds as shown in Formula I,
[0000]
[0000] in Formula I, R is selected from hydrogen, hydroxyl, and substituted or unsubstituted C 1 -C 30 hydrocarbyl, preferably from hydrogen, hydroxyl, and substituted or unsubstituted C 1 -C 20 alkyl, C 6 -C 30 aryl, C 6 -C 30 heteroaryl, C 7 -C 30 alkylaryl and C 7 -C 30 arylalkyl; R 1 and R 2 may be identical to or different from each other, independently selected from hydrogen and substituted or unsubstituted C 1 -C 30 hydrocarbyl, preferably from hydrogen and substituted or unsubstituted C 1 -C 20 alkyl, C 6 -C 30 aryl, C 7 -C 30 alkylaryl and C 7 -C 30 arylalkyl.
[0007] According to one embodiment of the present invention, R is selected from hydrogen, hydroxyl, C 1 -C 10 alkyl, and halogen or hydroxy substituted C 6 -C 10 aryl, C 6 -C 15 heteroaryl, C 7 -C 15 arylalkyl and C 7 -C 15 alkylaryl; R 1 and R 2 may be identical to or different from each other, and are selected from hydrogen, C 1 -C 10 alkyl and substituted or unsubstituted C 6 -C 20 aryl, C 7 -C 20 alkylaryl, and C 7 -C 20 arylalkyl.
[0008] According to the catalyst component (or be referred to as solid catalyst component, catalyst solid component) of the present invention, the substituted C 1 -C 30 hydrocarbyl, C 1 -C 20 hydrocarbyl, C 1 -C 20 alkyl, C 6 -C 30 aryl, C 6 -C 30 heteroaryl, C 7 -C 30 alkylaryl, C 7 -C 30 arylalkyl and so on mean that a hydrogen atom or carbon atom of these groups is substituted. For example, the hydrogen atom or carbon atom of the above mentioned hydrocarbyl, ring group, aryl, or alkylaryl and so on can be substituted by halogen, heteroatom (such as nitrogen atom, oxygen atom, etc.), hydroxy, alkyl, or alkoxy optionally. Said hydrocarbyl can contain a double bond and others as well.
[0009] According to another embodiment of the present invention, said internal electron donor A is at least one selected from compounds as shown in Formula II,
[0000]
[0010] R is selected from hydrogen, hydroxyl, and substituted or unsubstituted C 1 -C 30 hydrocarbyl, preferably from hydrogen, hydroxyl, and substituted or unsubstituted C 1 -C 20 alkyl, C 6 -C 30 aryl, C 6 -C 30 heteroaryl, C 7 -C 30 alkylaryl and C 7 -C 30 arylalkyl, more preferably from hydrogen, hydroxyl, C 1 -C 10 alkyl, and halogen or hydroxy substituted C 6 -C 10 aryl, C 6 -C 15 heteroaryl, C 7 -C 15 arylalkyl and C 7 -C 15 alkylaryl;
[0011] R 2 is selected from hydrogen, and substituted or unsubstituted C 1 -C 30 hydrocarbyl, preferably from hydrogen, and substituted or unsubstituted C 1 -C 20 alkyl, C 6 -C 30 aryl, C 7 -C 30 alkylaryl and C 7 -C 30 arylalkyl; more preferably from hydrogen, C 1 -C 10 alkyl, and substituted or unsubstituted C 6 -C 20 aryl, C 7 -C 20 alkylaryl and C 7 -C 20 arylalkyl;
[0012] R 3 -R 7 may be identical to or different from each other, each independently selected from hydrogen, halogen atoms, hydroxyl, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, C 6 -C 10 aryl, C 7 -C 12 alkylaryl, C 7 -C 12 arylalkyl, and C 2 -C 12 alkenyl, preferably from hydrogen, halogen atoms, hydroxyl, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, phenyl, C 7 -C 12 alkylphenyl, C 7 -C 12 phenyl alkyl, and C 2 -C 6 alkenyl; R 3 -R 7 can be optionally bonded together to form a ring.
[0013] It is known according to the present invention that, the compounds as shown in Formula I include those as shown in formula II. According to another embodiment of the catalyst component of the present invention, said internal electron donor A contains, but not limited to, N-butylidene aniline, 2,6-dimethyl-N-butylidene aniline, 4-chloro-N-butylidene aniline, N-(2-methylpropylidene)aniline, N-butylideneparabromoaniline, 2,6-diisopropyl-N-(2-methylpropylidene)aniline, 2,6-diisopropyl-N-butylidene aniline, 4-trifluoromethyl-N-butylidene aniline, 2,4, 6-trimethyl-N-butylidene aniline, N-(2-methylpropylidene)-1-butylamine, N-(2-methylpropylidene)-2-butylamine, N-hexylidene-1-hexylamine, N-hexylidene-1-octylamine, N-pentylidene-1-octylamine, 2,6-diisopropyl-N-heptamethyleneaniline, 2,6-diisopropyl-N-(2,2-diphenyl ethylidene)aniline, 2,6-dimethyl-N-(2,2-diphenyl ethylidene)aniline, N-(2-phenyl ethylidene)-8-amino quinoline, N-butylidene-3-amino quinoline, 2,6-dimethyl-N-hexylideneaniline, 2,6-diisopropyl-N-hexylideneaniline, 2,6-diisopropyl-N-(2-methylpropylidene)aniline, 2,6-dimethyl-N-(2-methylpropylidene)aniline, 2,6-diisopropyl-N-(diphenylmethylene)aniline, 2,6-dimethyl-N-(diphenylmethylene)aniline, 2,6-diisopropyl-N-(2-phenyl ethylidene)aniline, 2,6-dimethyl-N-(2-phenylethylidene)aniline, 4-methyl-N-(3-heptamethylene)aniline, N-heptamethyleneaniline, 2,6-diisopropyl-N-pentylideneaniline, 2,6-diisopropyl-N-(2-pentylidene)aniline, N-(3-pentylidene)-1-naphthylamine, N-(4-heptamethylene)-1-naphthylamine, 4-hydroxy-N-diphenylmethylene-1-naphthylamine, N-diphenylmethylenebenzylamine, N-(2-phenyl ethylidene)benzylamine, 2,6-dimethyl-N-(2,2-diphenyl ethylidene)aniline, 2,6-diisopropylN-(2,2-diphenyl ethylidene)aniline, N-(2,2-diphenyl ethylidene)aniline, N-(2,2-diphenyl ethylidene)-8-amino quinoline, N-(2,2-diphenyl ethylidene)-3-amino quinoline, 2-(phenylimino)methyl-4-tertiary butylphenol, 2-(phenylimino)methyl-4,6-ditertiary butylphenol, 2-(phenylimino)methyl-4-chlorophenol, 2-(phenylimino)methyl-4-fluorophenol, 2-(phenylimino)methyl-4,6-dichlorophenol, 2-(phenylimino)methyl-4-methylphenol, 2-(phenylimino)methyl-4-isopropylphenol, 2-(phenylimino)methylphenol, 2-(phenylimino)methyl-4-phenyl phenol, 2-(2,6-diisopropylphenylimino)methyl-4,6-dimethylphenol, 2-(2,6-diisopropylphenylimino)methyl-6-phenyl phenol, 2-(2,6-diisopropylphenylimino)methyl-4-isopropylphenol, 2-(butylimino)methyl-4-tertiary butylphenol, 2-(butylimino)methyl-4,6-ditertiary butylphenol, 2-(hexylimino)methyl-4-tertiary butylphenol, 2-(hexylimino)methyl-4,6-ditertiary butylphenol, 2-(octylimino)methyl-4-tertiary butylphenol, 2-(octylimino)methyl-4,6-ditertiary butylphenol, 2-(2,6-diisopropylphenylimino)methyl-4-tertiary butylphenol, 2-(2,6-diisopropylphenylimino)methyl-4,6-ditertiary butylphenol, 2-(phenylimino)methyl-4,6-ditertiary butylphenol, 2-(phenylimino)methyl-6-tertiary butylphenol, 2-(2,6-diisopropylphenylimino)methyl-4,6-dimethylphenol, 2-(2,6-dimethylphenylimino)methyl-4-ditertiary butylphenol, 2-(2,6-dimethylphenylimino)methyl-4,6-ditertiary butylphenol, N-(2-methoxy-5-tertiary butylphenylmethylene)-2,6-diisopropylaniline, N-(2-methoxy-5-tertiary butylphenylmethylene)-2,6-dimethylaniline, 2-(2,6-dimethylphenylimino)methyl-4-methoxy-6-tertiary butylphenol, N-phenylmethylene-2,6-diisopropylaniline, 2-(4-chlorophenylimino)methyl-4,6-ditertiary butylphenol, N-p-chlorophenylmethylene-2,6-diisopropylaniline, N-(4-tertiary butylphenylmethylene)-2,6-diisopropylaniline, N-phenylmethylene-2,6-dimethylaniline, N-(2,4-dichlorophenylmethylene)-2,6-dimethylaniline, N-(3,5-ditertiary butylphenylmethylene)aniline, N-(2,4, 6-trifluorophenylmethylene)-2,6-dimethylaniline, [2-(2,3,4,5,6-pentafluorophenylimino)methyl-4,6-ditertiary butylphenol, N-(2-methoxynaphthylmethylene)-2,6-diisopropylaniline, 2-(2,6-diisopropylphenylimino)methylphenol, 2-(2,6-dimethylphenylimino)methyl-6-tertiary butylphenol, 2-(2,6-diisopropylphenylimino)methyl-6-tertiary butylphenol, N-(2-methoxy-3-tertiary butylphenylmethylene)-2,6-diisopropylaniline, N-(3,5-ditertiary butylphenylmethylene)-1-naphthylamine, N-(3,5-ditertiary butylphenylmethylene)-2-naphthylamine, 2-(2-naphthylimino)methylphenol, 2-(4-quinolylimino)methyl-4,6-ditertiary butylphenol, 2-(3-quinolylimino)methyl-4,6-ditertiary butylphenol, 2-(8-quinolylimino)methyl-4,6-ditertiary butylphenol, N-(2-naphthylmethylene)-2,6-diisopropylaniline, N-(1-naphthylmethylene)-2,6-diisopropylaniline, N-(1-naphthylmethylene)-2,6-dimethylaniline, N-(2-anthrylmethylene)-2,6-diisopropylaniline, N-(1-anthrylmethylene)-2,6-dimethylaniline, 2-(2-benzylimino)-4,6-ditertiary butylphenol, 2-(3,5-ditertiary butyl-2hydroxy)benzylaminophenol, and 2-(3,5-ditertiary butyl-2hydroxy-benzylimino-1-naphthol.
[0014] According to the present invention, said internal electron donor A is an imine compound, the preparation method of which is a known technique. For example, it can be prepared by dissolving a aldehyde or ketone compound in an organic solvent, and then adding an amine to obtain an mixture, the mixture being refluxed under certain conditions (acidic or basic) for condensation to obtain a compound with the corresponding structure.
[0015] According to one embodiment of the catalyst component of the present invention, the weight content of internal electron donor A in the catalyst component is in a range of 0.01%-20% (eg. 0.05%-20% or 6%-20%), preferably 0.5%-15% (eg. 1%-15%), more preferably 2%-10%.
[0016] In the catalyst component, the content of titanium is in a range of 1.0 wt %-10.0 wt % (eg. 1.0-8.0 wt % or 1.5-10 wt %), preferably 2.0-6.0 wt % (eg. 2.0 wt %-5.0 wt %), more preferably 1.5 wt %-3.0 wt %; the content of magnesium is in a range of 5 wt %-50 wt % (eg. 10 wt %-40 wt %), preferably 10 wt %-30 wt % (eg. 20 wt %-30 wt %); the content of halogen is in a range of 10 wt %-70 wt % (eg. 30 wt %-70 wt %), preferably 40 wt %-60 wt % (eg. 52 wt %-60 wt %).
[0017] According to another embodiment of the present invention, the catalyst component further comprises internal electron donor B. In other words, the catalyst component contains magnesium, titanium, halogen, internal electron donor A, and internal electron donor B, wherein said internal electron donor B is at least one selected from the group consisting of esters, ethers, ketones, and amines, preferably from polycarboxylic acid ester compounds, diol ester compounds, and diether compounds.
[0018] In a preferred embodiment, the molar ratio of internal electron donor A to internal electron donor B is in a range from 1:10 to 10:1, preferably from 0.2:1 to 1:5, and more preferably from 0.5:1 to 2:1.
[0019] In the present invention, the polycarboxylic acid ester compounds include those disclosed in for example CN 85100997, the content of which is incorporated to the present invention as a reference. For example, said internal electron donor B is at least one selected from the group consisting of 2,3-bis(2-ethylbutyl)succinic acid diethyl ester, 2,3-diethyl-2-isopropylsuccinic acid diethyl ester, 2,3-diisopropylsuccinic acid diethyl ester, 2,3-ditertiary butylsuccinic acid diethyl ester, 2,3-diisobutylsuccinic acid diethyl ester, 2,3-(bistrimethylsilylalkyl)succinic acid diethyl ester, 2-(3,3,3-trifluoropropyl)-3-methyl succinic acid diethyl ester, 2,3-dineopentyl succinic acid diethyl ester, 2,3-diisopentyl succinic acid diethyl ester, 2,3-(1-trifluoromethyl-ethyl)succinic acid diethyl ester, 2-isopropyl-3-isobutyl succinic acid diethyl ester, 2-tertiary butyl-3-isopropyl succinic acid diethyl ester, 2-isopropyl-3-cyclohexyl succinic acid diethyl ester, 2-isopentyl-3-cyclohexyl succinic acid diethyl ester, 2,2,3,3-tetramethyl succinic acid diethyl ester, 2,2,3,3-tetraethyl succinic acid diethyl ester, 2,2,3,3-tetrapropyl succinic acid diethyl ester, 2,3-diethyl-2,3-diisopropyl disuccinic acid diethyl ester, 2,3-bis(2-ethylbutyl)succinic acid diisobutyl ester, 2,3-diethyl-2-isopropylsuccinic acid diisobutyl ester, 2,3-diisopropylsuccinic acid diisobutyl ester, 2,3-ditertiary butylsuccinic acid diisobutyl ester, 2,3-diisobutylsuccinic acid diisobutyl ester, 2,3-(bistrimethylsilylalkyl)succinic acid diisobutyl ester, 2-(3,3,3-trifluoropropyl)-3-methylsuccinic acid diisobutyl ester, 2,3-dineopentylsuccinic acid diisobutyl ester, 2,3-diisopentylsuccinic acid diisobutyl ester, 2,3-(1-trifluoromethyl-ethyl)succinic acid diisobutyl ester, 2-isopropyl-3-isobutyl succinic acid diisobutyl ester, 2-tertiary butyl-3-isopropylsuccinic acid diisobutyl ester, 2-isopropyl-3-cyclohexylsuccinic acid diisobutyl ester, 2-isopentyl-3-cyclohexylsuccinic acid diisobutyl ester, 2,2,3,3-tetramethylsuccinic acid diisobutyl ester, 2,2,3,3-tetraethylsuccinic acid diisobutyl ester, 2,2,3,3-tetrapropylsuccinic acid diisobutyl ester, 2,3-diethyl-2,3-diisopropyl disuccinic acid diisobutyl ester, diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, diisobutyl 2-methyl phthalate, di-n-butyl 2-methyl phthalate, diisobutyl 2-propyl phthalate, di-n-butyl 2-propyl phthalate, diisobutyl 2-butyl phthalate, din-butyl 2-butyl phthalate, diisobutyl 2-propyl phthalate, di-n-butyl 2-propyl phthalate, diisobutyl 4-propyl phthalate, di-n-butyl 4-butyl phthalate, diisobutyl 2-chloro phthalate, di-n-butyl 2-chloro phthalate, diisobutyl 4-chloro phthalate, di-n-butyl 4-chloro phthalate, and di-n-butyl 4-methoxy phthalate.
[0020] According to one embodiment of the catalyst component of the present invention, said internal electron donor B is at least one selected from the diol ester compounds as shown in Formula III:
[0000]
[0000] in Formula III, R 1 ′ and R 2 ′ may be identical to or different from each other, independently selected from C 1 -C 20 alkyl, C 6 -C 20 aryl, C 7 -C 20 arylalkyl, and C 7 -C 20 alkylaryl; R 3 ′-R 6 ′ may be identical to or different from each other, independently selected from hydrogen, C 1 -C 20 alkyl, C 6 -C 20 aryl, and C 2 -C 12 alkenyl; R I and R II may be identical to or different from each other, independently selected from hydrogen, C 1 -C 20 alkyl, C 1 -C 20 crycloalkyl, C 6 -C 20 aryl, C 7 -C 20 arylalkyl, C 9 -C 20 fused ring hydrocarbyl, and C 2 -C 2 alkenyl; R 3 ′, R 4 ′, R 5 ′, R 6 ′, R I , and R II can be optionally bonded together to form a ring; n is an intergar ranging from 0 to 10.
[0021] In a preferred embodiment, R 1 ′ and R 2 ′ may be identical to or different from each other, independently selected from C 1 -C 6 alkyl, phenyl, substituted phenyl, and cinnamyl; R 3 ′-R 6 ′ may be identical to or different from each other, independently selected from hydrogen, C 1 -C 6 alkyl, phenyl, substituted phenyl, and C 2 -C 6 alkenyl; R I and R II may be identical to or different from each other, independently selected from hydrogen, C 1 -C 6 alkyl, C 1 -C 6 crycloalkyl, benzyl, phenyl, substituted phenyl, naphthyl, and C 2 -C 6 alkenyl; n is an intergar ranging from 0 to 2; R 3 ′, R 4 ′, R 5 ′, R 6 ′, R I , and R II can be optionally bonded together to form a ring, and preferably form an alicyclic ring or aromatic ring (such as benzene ring, fluorine ring, naphthalene an so on). As used herein, when n is 0, it means that the carbon atom bonded with both R 3 ′ and R 4 ′ is directly bonded with another carbon atom (i.e. the one bonded with both R 5 ′ and R 6 ).
[0022] According to the present invention, the diol ester compounds are those commonly used in the art, for example those disclosed in CN101885789A, the content of which is incorporated to the present invention. Said internal electron donor B contains, but not limited to one or more of the following compounds: 2-isopropyl-1,3-dibenzoyloxy propane, 2-butyl-1,3-dibenzoyloxy propane, 2-cyclohexyl-1,3-dibenzoyloxy propane, 2-benzyl-1,3-dibenzoyloxy propane, 2-phenyl-1,3-dibenzoyloxy propane, 2-(1-naphthyl)-1,3-dibenzoyloxy propane, 2-isopropyl-1,3-diethylcarboxylpropane, 2-isopropyl-2-isopentyl-1,3-dibenzoyloxy propane, 2-isopropyl-2-isobutyl-1,3-dibenzoyloxy propane, 2-isopropyl-2-isopentyl-1,3-di(4-butylbenzoyloxy) propane, 2-isopropyl-2-isopentyl-1,3-dipropylcarboxyl propane, 2-isopropyl-2-butyl-1,3-dibenzoyloxy propane, 2-isopropyl-2-isopentyl-1-benzoyloxy-3-butylcarboxyl propane, 2-isopropyl-2-isopentyl-1-benzoyloxy-3-cinnamylcarboxyl propane, 2-isopropyl-2-isopentyl-1-benzoyloxy-3-ethylcarboxyl propane, 2,2-dicyclopentyl-1,3-phenylcarboxyl propane, 2,2-dicyclohexyl-1,3-phenylcarboxyl propane, 2,2-dibutyl-1,3-phenylcarboxyl propane, 2,2-diisobutyl-1,3-phenylcarboxyl propane, 2,2-diisopropyl-1,3-diphenylcarboxyl propane, 2,2-diethyl-1,3-diphenylcarboxyl propane, 2-ethyl-2-butyl-1,3-diphenylcarboxyl propane, 2,4-dibenzoyloxy pentane, 3-ethyl-2,4-dibenzoyloxy pentane, 3-methyl-2,4-dibenzoyloxy pentane, 3-propyl-2,4-dibenzoyloxy pentane, 3-isopropyl-2,4-dibenzoyloxy pentane, 2,4-di(2-propylbenzoyloxy) pentane, 2,4-di(4-propylbenzoyloxy) pentane, 2,4-di(2,4-dimethylbenzoyloxy) pentane, 2,4-di(2,4-dichlorobenzoyloxy) pentane, 2,4-di(4-chlorobenzoyloxy) pentane, 2,4-di(4-isopropylbenzoyloxy) pentane, 2,4-di(4-butylbenzoyloxy) pentane, 2,4-di(4-isobutylbenzoyloxy) pentane, 3,5-dibenzoyloxy heptane, 4-ethyl-3,5-dibenzoyloxy heptane, 4-propyl-3,5-dibenzoyloxy heptane, 4-isopropyl-3,5-dibenzoyloxy heptane, 3,5-di(4-propylbenzoyloxy) heptane, 3,5-di(4-isopropylbenzoyloxy) heptane, 3,5-di(4-isobutylbenzoyloxy) heptane, 3,5-di(4-butylbenzoyloxy) heptane, 2-benzoyloxy-4-(4-isobutylbenzoyloxy) pentane, 2-benzoyloxy-4-(4-butylbenzoyloxy) pentane, 2-benzoyloxy-4-(4-propylbenzoyloxy) pentane, 3-benzoyloxy-5-(4-isobutylbenzoyloxy) heptane, 3-benzoyloxy-5-(4-butylbenzoyloxy) heptane, 3-benzoyloxy-5-(4-propylbenzoyloxy) heptane, 9,9-dibenzoyloxymethyl fluorene, 9,9-di(propylcarboxylmethyl) fluorene, 9,9-di(isobutylcarboxylmethyl) fluorene, 9,9-di(butylcarboxylmethyl) fluorene, 9,9-dibenzoyloxymethyl-4-tertiary butyl fluorene, 9,9-dibenzoyloxymethyl-4-propyl fluorene, 9,9-dibenzoyloxymethyl-1, 2,3,4-tetrahydro fluorene, 9,9-dibenzoyloxymethyl-1, 2,3,4,5,6,7,8-octahydro fluorene, 9,9-dibenzoyloxymethyl-2, 3,6, 7-diphenylpropylindene, 9,9-dibenzoyloxymethyl-1, 8-dichloro fluorene, 7, 7-dibenzoyloxymethyl-2, 5-dinorbomadiene, 1, 4-dibenzoyloxy butane, 2,3-diisopropyl-1,4-dibenzoyloxy butane, 2,3-dibutyl-1, 4-dibenzoyloxy butane, 1,2-dibenzoyloxybeneze, 3-ethyl-1,2-dibenzoyloxybeneze, 4-n-butyl-1, 2-dibenzoyloxybeneze, 1,2-di(n-butylbenzoyloxy)benzene, 1,2-di(isopropylbenzoyloxy)benzene, 3-n-propyl-1,2-dibenzoyloxybeneze, 3-isopropyl-1,2-dibenzoyloxybeneze, 3-isobutyl-1,2-dibenzoyloxybeneze, 3-n-propyl-1,2-di(n-propylbenzoyloxy)benzene, 3-propyl-1,2-di(n-butylbenzoyloxy)benzene, 3-isopropyl-1,2-di(n-propylbenzoyloxy)benzene, 3-isopropyl-1,2-di(n-butylbenzoyloxy)benzene, 3-isopropyl-1,2-di(isopropylbenzoyloxy)benzene, 3-isobutyl-1,2-di(n-propylbenzoyloxy)benzene, 3-isobutyl-1,2-di(n-butylbenzoyloxy)benzene, 3-isobutyl-1,2-di(isopropylbenzoyloxy)benzene, 3-propyl-1,2-di(n-propylbenzoyloxy)benzene, 1,8-dibenzoyloxynaphthalene, 2-ethyl-1,8-dibenzoyloxynaphthalene, 2-propyl-1,8-dibenzoyloxynaphthalene, 2-butyl-1,8-dibenzoyloxynaphthalene, 4-butyl-1,8-dibenzoyloxynaphthalene, 4-isobutyl-1,8-dibenzoyloxynaphthalene, 4-isopropyl-1,8-dibenzoyloxynaphthalene, 2-propyl-1,8-dibenzoyloxynaphthalene, and 4-propyl-1,8-dibenzoyloxynaphthalene.
[0023] According to the present invention, the diether compounds can also be diether compounds commonly used in the art, for example, 1,3-diether compounds. Preferably, said internal electron donor B is at least one selected from the diether compounds as shown in Formula IV:
[0000]
[0000] in Formula IV, R 8 and R 9 may be identical to or different from each other, independently selected from C 1 -C 20 alkyl; R III -R VI may be identical to or different from each other, independently selected from hydrogen, C 1 -C 20 alkyl, C 1 -C 20 cycloalkyl, C 6 -C 20 aryl, C 6 -C 20 alkylaryl, C 6 -C 20 arylalkyl, and C 2 -C 12 alkenyl, and R III -R VI can be optionally bonded together to form a ring; n is an intergar ranging from 0 to 10.
[0024] Preferably, R 8 and R 9 may be identical to or different from each other, independently selected from C 1 -C 6 alkyl; R III -R VI may be identical to or different from each other, independently selected from hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, phenyl, substituted phenyl, benzyl, naphthalene, and C 2 -C 6 alkenyl; n is an intergar ranging from 0 to 2; R III -R VI can be optionally bonded together to form a ring, preferably form an alicyclic ring or aromatic ring. When n is 0, it means that the carbon atom bonded with both R V and OR 8 is directly bonded with another carbon atom (i.e. the one bonded with both OR 9 and R IV ).
[0025] According to the present invention, said internal electron donor B contains but not limited to one or more of the following compounds: 2-isopropyl-1,3-dimethoxy propane, 2-butyl-1,3-dimethoxy propane, 2-cyclohexyl-1,3-dimethoxy propane, 2-benzyl-1,3-dimethoxy propane, 2-phenyl-1,3-dimethoxy propane, 2-(1-naphthyl)-1,3-dimethoxy propane, 2-isopropyl-2-isopentyl-1,3-dimethoxy propane, 2-isopropyl-2-isobutyl-1,3-dimethoxy propane, 2-isopropyl-2-butyl-1,3-dimethoxy propane, 2,2-dicyclopentyl-1,3-dibenzoyloxypropane, 2,2-dicyclohexyl-1,3-dimethoxy propane, 2,2-dibutyl-1,3-dimethoxy propane, 2,2-diisobutyl-1,3-dimethoxy propane, 2,2-diisopropyl-1,3-dimethoxy propane, 2,2-diethyl-1,3-dimethoxy propane, 2-ethyl-2-butyl-1,3-dimethoxy propane, 2,4-dimethoxy pentane, 3-ethyl-2,4-dimethoxy pentane, 3-methyl-2,4-dimethoxy pentane, 3-propyl-2,4-dimethoxy pentane, 3-isopropyl-2,4-dimethoxy pentane, 3,5-dimethoxy heptane, 4-ethyl-3,5-dimethoxy heptane, 4-propyl-3,5-dimethoxy heptane, 4-isopropyl-3,5-dimethoxy heptane, 9,9-dimethoxymethyl fluorene, 9,9-dimethoxymethyl-4-tertiary butyl fluorene, 9,9-dimethoxymethyl-4-propyl fluorene, 9,9-dimethoxymethyl-1, 2,3,4-tetrahydro fluorene, 9,9-dimethoxymethyl-1, 2,3,4,5,6,7, 8-octahydro fluorene, 9,9-dimethoxymethyl-2,3,6, 7-diphenylpropylindene, 9,9-dimethoxymethyl-1,8-dichloro fluorene, 7, 7-dimethoxymethyl-2, 5-dinorbomadiene, 1, 4-dimethoxy butane, 2,3-diisopropyl-1,4-dimethoxy butane, 2, 3-dibutyl-1,4-dimethoxy butane, 1,2-dimethoxybeneze, 3-ethyl-1, 2-dimethoxybeneze, 4-butyl-1,2-dimethoxybeneze, 1, 8-dimethoxynaphthalene, 2-ethyl-1,8-dimethoxynaphthalene, 2-propyl-1,8-dimethoxynaphthalene, 2-butyl-1,8-dimethoxynaphthalene, 4-butyl-1,8-dimethoxynaphthalene, 4-isobutyl-1,8-dimethoxynaphthalene, 4-isopropyl-1,8-dimethoxynaphthalene, and 4-propyl-1,8-dimethoxynaphthalene.
[0026] According to another embodiment of the catalyst component of the present invention, the weight content of said internal electron donor B in the catalyst component is in a range of 0.01-20%, preferably 1-15%.
[0027] According to another aspect of the present invention, provided is a preparation method of the catalyst component as above described, comprising the following steps: contacting at least one magnesium compound and at least one titanium compound with at least one internal electron donor compound, so as to prepare the catalyst component, wherein the internal electron donor compound comprises internal electron donor A, and optionally, internal electron donor B, and internal electron donor A is at least one selected from the compounds as shown in Formula I.
[0028] According to the present invention, the internal electron donor compound can include internal electron donor B or not internal electron donor B.
[0029] According to the present invention, the magnesium compound is selected from the group consisting of magnesium dihalide, alkoxy magnesium, alkyl magnesium, hydrate or alcohol adduct of magnesium dihalide, or one of the derivatives formed by replacing a halogen atom of the magnesium dihalide molecular formula with an alkoxy or haloalkoxy group, or their mixture. Preferred magnesium compounds are magnesium dihalide, alcohol adduct of magnesium dihalide, and alkoxy magnesium.
[0030] According to the present invention, the titanium compound is as shown in Formula of TiX n (OR) 4-n , in which R is C 1 -C 20 hydrocarbyl group, X is halogen, and n=0-4. For example, it can be titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxy titanium, tetraethoxy titanium, triethoxy titanium chloride, diethoxy titanium dichloride and ethoxy titanium trichloride.
[0031] According to one embodiment of the method of the present invention, calculated in per mole of magnesium, the adding amount of internal electron donor A is in a range from 0.001 mol to 10 mol (eg. 0.001 mol-10 mol), preferably from 0.001 mol to 5 mol, more preferably from 0.01 mol to 3 mol; and/or the adding amount of internal electron donor B is in a range from 0 mol to 10 mol (eg. 0.001 mol-10 mol), preferably from 0 mol to 5 mol (eg. 0.001 mol-5 mol), more preferably 0.01 mol to 3 mol (eg. 0.02 mol-3 mol).
[0032] According to the present invention, the methods for preparing the catalyst component include, but not limited to any one of the following methods.
[0033] Method 1: According to another embodiment of the catalyst component of the present invention, the catalyst can be prepared by the method comprising the following steps.
[0034] 1) A magnesium compound is dissolved in a solvent system comprising an organic epoxy compound, an organic phosphorus compound and an inert diluent. After a uniform solution is formed, the solution is mixed with a titanium compound, and solids are precipitated at the presence of a coprecipitation agent.
[0035] 2) Such solids are treated with an internal electron donor compound which contains internal electron donor A as shown in Formula I so that said internal electron donor compound is loaded on the solids; optionally, titanium tetrahalide and inert diluent are used to further treat the solids to obtain the catalyst component.
[0036] According to one embodiment, the internal electron donor compound can contain internal electron donor compound B in addition to internal electron donor A as shown in Formula I. Said internal electron donor B is at least one selected from the group consisting of esters, ethers, ketones, and amines. Preferably said internal electron donor B is selected from polycarboxylic acid ester compounds, diol ester compounds, and diether compounds. When internal electron donor compound B is used, the solids obtained from step 1) can be firstly treated with internal electron donor compound B, so that said internal electron donor compound is loaded on the solids, and then titanium tetrahalide and inert diluent are used to further treat the solids followed by treating with internal electron donor A, to obtain the catalyst component.
[0037] There is no special restriction to the coprecipitation agent used in the method of the present invention, as long as it can precipitate the solid. The coprecipitation agent can be selected from organic acid anhydrides, organic acids, ethers, and ketone, or their mixtures. Examples of the organic acid anhydrides are as follows: acetic anhydride, phthalic anhydride, butanedioic anhydride, and maleic anhydride. Examples of the organic acid are as follows: acetic acid, propionic acid, butyric acid, acrylic acid, and methacrylic acid. Examples of the esters are as follows: dibutyl phthalate, diphen 2,4-pentandiol dibenzoate, 3-ethyl-2,4-pentandiol dibenzoate, 2,3-diisopropyl-1,4-butandiol dibenzoate, 3,5-heptandiol dibenzoate, and 4-ethyl-3,5-heptandiol dibenzoate. Examples of the ethers are as follows: dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, 2-isopropyl-2-isopentyldimethoxy propane, and 9,9-(dimethoxymethyl) fluorene. The ketone can be at least one of acetone, methyl ethyl ketone and benzophenone.
[0038] In the present invention, the organic epoxides contain at least one selected group consisting of C2-C8 aliphatic olefins, dialkenes, halogenated aliphatic olefins, oxide of dialkenes, glycidyl ethers and inner ethers. Certain specific compounds are as follows: ethylene oxide, propylene oxide, butylenes oxide, butadiene oxide, butadiene dioxide, epoxy chloropropane, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran, and so on.
[0039] In the present invention, the organic phosphorus compound can be hydrocarbyl ester or halogenated hydrocarbyl ester of orthophosphoric acid or phosphorous acid, specifically, such as, trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenylmethyl phosphate. Triphenylmethyl phosphate is preferred.
[0040] In the present invention, the inert diluents can be at least one selected from C 6 -C 10 alkane or aromatic hydrocarbon, preferably from hexane, heptane, octane, decane, benzene, toluene, xylene, or derivatives thereof.
[0041] According to one embodiment of the method of the present invention, calculated based on per mole magnesium, the dosage of the organic epoxide is in a range of 0.2 mol-10 mol, the dosage of the organic phosphorus compound is in a range of 0.1 mol-3 mol, the dosage of the titanium compound is in a range of 0.2 mol-50 mol, and the dosage of the coprecipitation agent is in a range of 0 mol-15 mol.
[0042] According to one embodiment of the method of the present invention, the recitation, “optionally, titanium tetrahalide and inert diluent are used to further treat the solids” means that a titanium compound and/or inert diluent can be used to treat the solids as required.
[0043] According to the present invention, the involved ranges, such as the definition for the groups, contents, or dosages and the like, each contain any specific defined value between the up limit value and the low limit value, and a range between any two values selected from the range between the up limit value and the low limit value.
[0044] Method 2: A magnesium halide is dissolved in a uniform solution formed by an organic epoxide and organic phosphorus compound. An inert solvent can also be added, and then an internal electron donor compound is added. The resulting solution is mixed with a titanium compound, kept at a low temperature for a period of time to precipitate the carries. Then the temperature is increased by heating. The mixture is treated with a titanium compound or an inert solvent, filtered, washed, and dried to obtain a solid catalyst comprising titanium, magnesium, halogen and electron donor. The internal electron donor compound comprises internal electron donor A as shown in Formula I.
[0045] According to one embodiment, the internal electron donor compound can contain internal electron donor compound B in addition to internal electron donor A as shown in Formula I. Said internal electron donor B is at least one selected from the group consisting of esters, ethers, ketones, and amines. Preferably said internal electron donor B is selected from polycarboxylic acid ester compounds, diol ester compounds, and diether compounds. The dosage of the solvent and the titanium compound is the conventional dosage, and will not be explained herein in detail.
[0046] Method 3: The method comprises the following steps.
[0047] 1) A magnesium compound and an alcohol compound are mixed with an inert solvent. Then a coprecipitation agent is added to obtain an alcohol adduct.
[0048] 2) The alcohol adduct is contacted with a titanium compound solution at a low temperature, and then solid particles are obtained by separation.
[0049] 3) The solid particles obtained in step 2) are added to a titanium compound solution, and then solid particles are obtained by separation.
[0050] 4) The solid particles obtained in step 3) are washed by an inert solvent, and dried to obtain the catalyst component.
[0051] In the method, the internal electron donor compound is added in any one of steps 1) to 4). The internal electron donor compound comprises internal electron donor A as shown in Formula I.
[0052] According to one embodiment, internal electron donor A as shown in Formula I is added in step 2) and/or 4). For example, the internal electron donor compound is added after the contacting of the alcohol adduct with the titanium compound in step 2), and/or after the separation of the solid in step 3). When the compound as shown in Formula I is added, the treatment temperature is in a range of 60-100° C., preferably 80-100° C., and the treatment time is in a range of 0.5-3 hours, preferably 0.5-2 hours.
[0053] According to another embodiment, the internal electron donor compound can contain internal electron donor compound B in addition to internal electron donor A as shown in Formula I. Said internal electron donor B is at least one selected from the group consisting of esters, ethers, ketones, and amines. Preferably said internal electron donor B is selected from polycarboxylic acid ester compounds, diol ester compounds, and diether compounds.
[0054] In one embodiment of the above catalyst component, in step 1), preferably, the organic alcohol compound and the magnesium compound (in a molar ratio of 2:1-5:1) are mixed with the inert solvent. After the temperature is increased to 120-150° C., the coprecipitation agent is added in a molar ratio of coprecipitation agent to magnesium of 5:1-50:1. The reaction is carried for 1-5 hours.
[0055] In another embodiment of the above catalyst component, the low temperature refers to a temperature below 0° C. Preferably, the alcohol adduct is contacted with the titanium compound solution in a molar ratio of titanium to magnesium of 10:1-50:1 at a low temperature from −15° C. to −40° C. After the temperature is increased to 90-110° C., the internal electron donor compound is added in a molar ratio of magnesium to internal electron donor of 2:1-10:1. The reaction is carried out at 100-130° C. for 1-3 hours, and then the solid particles are obtained by filtration.
[0056] In another embodiment of the above catalyst component, preferably, in step 3), the solid particles are added to the titanium compound in a molar ratio of titanium to magnesium with stirring. The reaction is carried out at 100-130° C. for 1-3 hours, and then the solid particles are obtained by filtration.
[0057] The inert solvent comprises at least one of C 1 -C 20 alkane, cycloalkane, and aromatic hydrocarbon. The dosage of the inert solvent is a conventional dosage in the art.
[0058] Method 4: The method comprises the following steps.
[0059] 1) A magnesium halide alcohol adduct is dispersed in a dispersion system to form an emulsion. The emulsion is discharged into a cooling liquid for chilling, so as to form magnesium chloride alcohol adduct microparticles, which are spherical carriers.
[0060] 2) A titanium compound is used to treat the above spherical carriers. The temperature is gradually increased. An internal electron donor compound is added before or after the treatment with the titanium compound, to obtain the spherical catalyst component.
[0061] In the method, the internal electron donor compound comprises internal electron donor A as shown in Formula I.
[0062] According to one embodiment, the internal electron donor compound can contain internal electron donor compound B in addition to internal electron donor A as shown in Formula I. Said internal electron donor B is at least one selected from the group consisting of esters, ethers, ketones, and amines. Preferably said internal electron donor B is selected from polycarboxylic acid ester compounds, diol ester compounds, and diether compounds.
[0063] According to one embodiment of the method of the present invention, the magnesium halide alcohol adduct is as shown in MgX 2 .nROH, wherein R is C 1 -C 4 alkyl, n is in a range of 1.5-3.5, preferably 2.0-3.0; X is halogen, preferably chloro, bromo, or iodo. The magnesium halide alcohol adduct is prepared by the reaction of magnesium dihalide and an alcohol at a certain temperature. The magnesium halide alcohol adduct has a particle size of 10-300 micrometers, preferably 30-100 micrometers.
[0064] According to another embodiment of the method of the present invention, in step 2), preferably, an excess amount of titanium compound is used to treat the above spherical carriers at a low temperature. The molar ratio of the titanium compound to the magnesium halide ranges from 20 to 200, preferably from 30 to 60. The onset treatment temperature is in a range from −30° C. to 0° C., preferably from −25° C. to −20° C. The final treatment temperature is in a range from 80° C. to 136° C., preferably from 100° C. to 130° C.
[0065] According to the method of the present invention, the dispersion system uses hydrocarbon inert solvent, such as kerosene, paraffin oil, petrolatum oil, white oil, etc. A surfactant or organosilicon compound can also be added. In one embodiment of the present invention, a combination of white oil and silicone oil is used as the dispersion system. The cooling liquid is an inert hydrocarbon solvent with low point, such as petroleum ether, pentane, hexane, heptane and the like. The inert solvent comprises C 1 -C 20 alkane, cycloalkane or aromatic hydrocarbon or a mixture thereof. The dosage of the dispersion system i.e. the cooling liquid is the conventional dosage in the art.
[0066] In a specific example, the magnesium alcohol adduct microparticles can be subjected to washing and drying before being treated in step 2). The catalyst component of step 2) can be washed by an inert solvent to obtain a catalyst component with a better effect. The inert solvent can be selected from those commonly used, such as C 1 -C 20 alkane, cycloalkane or aromatic hydrocarbon or a mixture thereof.
[0067] In specific example, based on the alcohol adduct of magnesium halide, the dosage of the titanium compound is in a range of 1 mol-100 mol, preferably 10 mol-60 mol.
[0068] According to the catalyst component of the present invention, when the inert solvent is used for washing, the content of the inert solvent in the catalyst component can be in a range of 1 wt %-15 wt %. The catalyst component has a specific surface greater than 250 m 2 /g.
[0069] Method 5: An alkoxy magnesium or alkoxy magnesium chloride is suspended in an inert solvent to form a suspension, which is then mixed and contacted with a titanium compound to obtain a solid. The solid is then contacted with the internal electron donor comprising the compound as shown in Formula I, so as to obtain a solid catalyst comprising titanium, magnesium, halogen, and electron donor. According to one embodiment, the internal electron donor compound can contain internal electron donor compound B in addition to internal electron donor A as shown in Formula I. Said internal electron donor B is at least one selected from the group consisting of esters, ethers, ketones, and amines. Preferably said internal electron donor B is selected from polycarboxylic acid ester compounds, diol ester compounds, and diether compounds. The alkoxy magnesium is at least one selected from the group consisting of diethyoxyl magnesium, dipropyloxyl magnesium, dihexyloxyl magnesium, dipentyloxy magnesium, and dioctyloxyl magnesium. The alkoxy magnesium chloride is at least one selected from the group consisting of ethyl magnesium chloride, propyl magnesium chloride, pentyl magnesium chloride, hexyl magnesium chloride, heptyl magnesium chloride, and octyl magnesium chloride. The dosage of the inert solvent is conventional.
[0070] According to another aspect of the present invention, provided is a catalyst used for propene polymerization, comprising a reactant of the following components:
[0071] a). the catalyst component as described above or the catalyst component prepared by the method as described above;
[0072] b). an organoaluminium compound; and
[0073] c). optionally, an organosilicon compound.
[0074] According to the catalyst used for propene polymerization of the present invention, the organoaluminium compound as a cocatalyst can be selected from those which can be used as a cocatalyst of Ziegler-Natta catalyst in the filed of propene polymerization. Preferably, the organoaluminium compound is selected from the compounds as show in formula AlR′ n X 3-n , wherein R′ is selected from hydrogen and C 1 -C 20 hydrocarbyl; X is halogen, and n is an intergar ranging from 1 to 3.
[0075] In the above catalyst, the organoaluminium compound is at least one selected from the following compounds: trimethyl aluminium, triethyl aluminium, triisobutyl aluminium, trioctyl aluminium, diethylaluminium hydride, diisobutylaluminium hydride, diethylaluminium chloride, diisobutylaluminium chloride, ethyl aluminium sesquichloride, and ethyl aluminium dichloride. Triethyl aluminium and/or triisobutyl aluminium is more preferable.
[0076] In the above catalyst, the dosage of the organoaluminium compound can be a conventional dosage in the art. Generally, the molar ratio of organoaluminium compound b) to catalyst component a) is in a range of 20-800:1, calculated based on the ratio of aluminium to titanium.
[0077] In the above catalyst, “optionally, an organosilicon compound” means that the catalyst may contain a reactant of components a) and b), or a reactant of components a), b), and c). According to the propene polymerization catalyst of the present invention, the external electron donor component can be a variety of external electron donors known in the art.
[0078] In the above catalyst, the external electron donor organosilicon compound is preferably a compound as shown in formula of R 3 m Si(OR 4 ) 4-m , wherein, 0≦m≦3, R 3 and R 4 can be alkyl, cycloalkyl, aryl, halogenated alkyl, or amino, independently, and R 3 can also be halogen or hydrogen. Preferably, the organosilicon compound is at least one selected from the following organosilicon compounds: trimethylmethoxysilicane, trimethylethyoxylsilicane, trimethylphenoxysilicane, dimethyldimethoxysilicane, dimethyldiethyoxylsilicane, cyclohexylmethyldiethyoxylsilicane, methylcyclohexyldimethoxysilicane, diphenyl dimethoxysilicane, diphenyl diethyoxylsilicane, phenyl triethyoxylsilicane, phenyl trimethoxysilicane, and vinyltrimethoxysilicane, preferably selected from cyclohexylmethyldimethoxysilicane and diisopropyldimethoxysilicane. These organosilicon compounds can be used separately or in a combination of two or three compounds.
[0079] According to the catalyst for propene polymerization of the present invention, there is no restriction to the dosage of the external electron donor. Preferably, the molar ratio of the organosilicon compound c) to the catalyst component a) is in a range of 0-100:1, based on the molar ratio of silicon to titanium.
[0080] According to another aspect of the present invention, provided is a prepolymerization catalyst for propene polymerization, comprising a prepolymer obtained by pre-polymerization of propene with the catalyst component. Preferably, multiple of the pre-polymerization is in a range of 0.1 g-1000 g of propene polymer per 1 g of the catalyst component. Prepolymerization can be performed in gas phase or liquid phase according to the known technique. The steps of prepolymerization as a part of the process of continuous polymerization can be performed on line, and also can be separately performed in batches.
[0081] According to another aspect of the present invention, provided is a method for propene polymerization, comprising the step of polymerization of propene which is performed in the presence of the catalyst component as described above, the catalyst as described above, or the pre-polymerization catalyst as described above, wherein said polymerization comprises homopolymerization and copolymerization. The prepolymerization process can be carried out, according to the known technique, in liquid phase or gas phase, or a stage combination thereof. The prepolymerization process can be used not only for propene homopolymerization but also for propene copolymerization.
[0082] According to the present invention, when copolymerization is performed, the comonomer is as shown in the formula of CH 2 ═CHR, wherein R is hydrogen or C 1 -C 12 hydrocarbyl, preferably hydrogen or C 1 -C 6 alkyl. For example, the comonomer is preferably at least one selected from the group consisting of ethylene, 1-n-butene, 1-n-pentene, 1-n-hexylene, 1-n-octylene, and 4-methyl-1-pentene.
[0083] According to the present invention, when the imine compound as shown in Formula I is used as the internal electron donor compound for propene polymerization, it can interact with active component such as titanium and magnesium, to form multi active site. In this manner, the catalyst has a high catalytic activity and a slow rate of delay of activity, and the obtained polymer has a high melt index, wide molecular weight distribution and high isotacticity. According to the present invention, the catalyst has a high catalytic activity, excellent stability and good hydrogen response. The fluidity and processability of the obtained polymer are good. The catalyst component and the catalyst and so on provided by the present invention have a wide application prospect.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0084] The present invention will be explained in detail below in combination with the embodiments. It should be noted that the embodiments are provided for illustrating, rather than restricting the present invention.
Testing Method
[0085] 1. Isotacticity of the polymer (%): measured by boiling heptane extraction.
[0086] 2. Melt index of the polymer (g/10 min): measured based on ASTMD1238-99 standard.
[0087] 3. Molecular weight distribution of polymer (Mw/Mn): measured by a gel permeation chromatograph manufactured by Waters company, with 1,2,4-trichlorobenzene as solvent, and styrene as standard sample.
[0088] 4. Nuclear magnetic resonance (NMR) analysis about the polymer: H-NMR of the polymer is measured by using a Bruke dmx 300 MHz NMR spectrometer at a temperature of 275 K, with deuterated chloroform as solvent, TMS as internal standard.
[0089] Specific synthesis of some of imine compounds is provided in the following text as examples.
I. Synthesis of Compounds
Compound 1
[0090] 1.9 g of 2,2-diphenylacetaldehyde and 100 mL of isopropanol were placed into a three-neck flask. 2,6-diisopropylaniline (1.92 g) and 0.1 mL of glacial acetic acid were added into the mixture with stirring. The resulting mixture was stirred and reacted at room temperature for 2 hours, and then heated to perform a reflux reaction for 24 hours. After cooling, a solid was precipitated, which was then recrystallized by using a mixed solvent of diethyl ether and ethanol, to obtain a product 2,6-diisopropyl-N-(2,2-diphenylethylidene)aniline (1.52 g; the yield was 71%). 1 H-NMR (δ, ppm, TMS, CDCl 3 ): 7.86-7.55 (10H, m, ArH), 7.42 (1H, s, CH═N), 7.12-7.28 (3H, ArH), 4.46 (1H, m, CH), 3.20-3.36 (2H, m, CH), 1.23-1.36 (6H, d, CH 3 ), 0.98-1.20 (6H, d, CH 3 ); mass spectrum, FD-mass spectrometry: 355.
Compound 2
[0091] 1.2 g of phenylacetaldehyde and 80 mL of methanol were placed into a three-neck flask. 2,6-diisopropyl aniline (1.93 g) and 0.1 mL of glacial acetic acid were added into the mixture with stirring. The resulting mixture was stirred and reacted at room temperature for 4 hours, and then heated to perform a reflux reaction for 32 hours, followed by cooling to room temperature. The solvent was removed. The primary product was purified by using a silica gel column, with ethyl acetate/petroleum ether (1:50) as an eluant, to obtain a product 2,6-diisopropyl-N-(2-phenylethylidene) aniline (2.12 g; the yield was 76%). 1 H-NMR (δ, ppm, TMS, CDCl 3 ): 7.76-7.55 (5H, m, ArH), 7.46 (1H, s, CH═N), 7.12-7.28 (3H, ArH), 4.16 (2H, s, CH 2 ), 3.42-3.65 (2H, m, CH), 1.23-1.36 (6H, d, CH 3 ), 0.98-1.20 (6H, d, CH 3 ); mass spectrum, FD-mass spectrometry: 279.
Compound 3
[0092] 1.2 g of phenylacetaldehyde and 80 mL of ethanol were placed into a three-neck flask. 8-aminoquinoline (1.44 g) and 0.1 mL of glacial acetic acid were added into the mixture with stirring. The resulting mixture was stirred and reacted at room temperature for 2 hours, and then heated to perform a reflux reaction for 30 hours, followed by cooling to room temperature. The solvent was removed. The primary product was separated and purified by using a silica gel column, with ethyl acetate/petroleum ether (1:30) as an eluant, to obtain a product N-(2-phenylethylidene)-8-aminoquinoline (2.08 g; the yield was 85%). 1 H-NMR (δ, ppm, TMS, CDCl 3 ): 8.60-8.86 (1H, m, ArH), 7.96-7; 65 (5H, m, ArH), 7.60-7.56 (5H, m, ArH), 7.46 (1H, m, CH═N), 2.86 (2H, m, CH 2 ); mass spectrum, FD-mass spectrometry: 246.
Compound 4
[0093] 1.9 g of 2,2-diphenylacetaldehyde, 0.1 mL of glacial acetic acid, and 80 mL of isopropanol were placed into a three-neck flask. A mixed solution of 2,6-dimethylaniline (1.33 g) and 10 mL of isopropanol was added into the mixture with stirring. The resulting mixture was stirred and reacted at room temperature for 1 hour, and then heated to perform a reflux reaction for 24 hours, followed by removing the solvent. The primary product was purified by using a silica gel column, with ethyl acetate/petroleum ether (1:30) as an eluant, to obtain a product 2,6-dimethyl-N-(2,2-diphenylethylidene) aniline of 1.82 g (the yield was 64%). 1 H-NMR (δ, ppm, TMS, CDCl 3 ): 7.86-7.55 (10H, m, ArH), 7.42 (1H, s, CH═N), 7.12-7.28 (3H, ArH), 4.46 (1H, m, CH), 2.42-2.65 (6H, s, CH 3 ); mass spectrum, FD-mass spectrometry: 299.
Compound 5 Synthesis of compound 2-(4-quinolylimino)methyl-4,6-di-tert-butylphenol
[0094] 2.34 g of 3,5-di-tert-butylsalicylaldehyde and 70 mL of ethanol were placed into a reaction flask. 1.44 g of 4-aminoquinoline and 0.1 mL of glacial acetic acid were added into the mixture with stirring. The resulting mixture was stirred and reacted for 0.5 hour, and then heated to 100° C. to perform a reflux reaction for 24 hours, followed by removing the solvent. The primary product was purified by using a silica gel column, with ethyl acetate/petroleum ether (1:30) as an eluant, to obtain a product [2-(4-quinolylimino)methyl-4,6-di-tert-butylphenol] of 2.5 g. The yield was 70%. 1 H-NMR (δ, ppm, TMS, CDCl 3 ): 8.60-8.76 (2H, m, CH═N), 7.96-7.65 (4H, m, ArH), 7.60-7.36 (3H, m, ArH), 3.73 (1H, s, OH), 1.30-1.54 (18H, m, CH 3 ); mass spectrum, FD-mass spectrometry: 360.
Compound 6 Synthesis of compound 2-(8-quinolylimino)methyl-4,6-di-tert-butylphenol
[0095] 2.34 g of 3,5-di-tert-butylsalicylaldehyde and 70 mL of ethanol were placed into a reaction flask. 1.44 g of 8-aminoquinoline and 0.1 mL of glacial acetic acid were added into the mixture with stirring. The resulting mixture was stirred and reacted for 1 hour, and then heated to 100° C. to perform a reflux reaction for 24 hours, followed by removing the solvent. The primary product was purified by using a silica gel column, with ethyl acetate/petroleum ether (1:30) as an eluant, to obtain a product [2-(8-quinolylimino)methyl-4,6-di-tert-butylphenol] of 2.8 g. The yield was 80%. 1 H-NMR (δ, ppm, TMS, CDCl 3 ): 8.60-8.76 (2H, m, CH═N), 7.96-7.65 (4H, m, ArH), 7.60-7.36 (3H, m, ArH), 3.74 (1H, s, OH), 1.30-1.54 (18H, m, CH 3 ); mass spectrum, FD-mass spectrometry: 360.
Compound 7 Synthesis of compound 2-(hexylimino)methyl-4,6-di-tert-butylphenol
[0096] 2.34 g of 3,5-di-tert-butylsalicylaldehyde and 70 mL of isopropanol were placed into a reaction flask. 1-hexyl amine (1.01 g) and 0.1 mL of glacial acetic acid were added into the mixture with stirring. The resulting mixture was stirred and reacted for 0.5 hour, and then heated to 100° C. to perform a reflux reaction for 20 hours, followed by removing the solvent. The primary product was purified by using a silica gel column, with ethyl acetate/petroleum ether (1:30) as an eluant, to obtain a product [2-(hexylimino)methyl-4,6-di-tert-butylphenol] of 2.7 g. The yield was 67.7%. 1 H-NMR (δ, ppm, TMS, CDCl 3 ): 8.60-8.76 (1H, m, CH═N), 7.64-7.36 (2H, m, ArH), 3.74 (11H, s, OH), 2.78 (2H, m, ═NCH 2 ), 1.33-1.54 (18H, m, CH 3 ), 1.25-1.31 (8H, m, CH 2 ), 0.89-1.08 (3H, t, CH 3 ); mass spectrum, FD-mass spectrometry: 317.
Compound 8 Synthesis of compound N-(1-naphthylmethylene)-2,6-diisopropyl aniline
[0097] 1.56 g of 1-naphthoic aldehyde and 80 mL of isopropanol were placed into a reaction flask. 2,6-diisopropylphenylimine (1.78 g) and 0.1 mL of glacial acetic acid were added into the mixture with stirring. The resulting mixture was stirred and reacted for 0.5 hour, and then heated to perform a reflux reaction for 24 hours, followed by removing the solvent. The primary product was purified by using a silica gel column, with ethyl acetate/petroleum ether (1:30) as an eluant, to obtain a product [N-(1-naphthylmethylene)-2,6-diisopropyl aniline] (2.14 g; the yield was 68%). 1H-NMR (δ, ppm, TMS, CDCl3): 8.60-8.76 (1H, m, CH═N), 7.86-8.02 (2H, m, ArH), 7.64-7.36 (5H, m, ArH), 7.08-7.28 (3H, m, ArH), 3.16-3.34 (2H, s, CH), 1.32-1.52 (6H, m, CH 3 ), 1.23-1.32 (6H, m, CH 3 ); mass spectrum, FD-mass spectrometry: 315.
II. Preparation of Catalyst Component and Polymerization of Propylene
Group 1
Examples and Comparative Examples
Example 1
(1) Preparation of a Solid Catalyst Component (Namely Catalyst Component)
[0098] 4.8 g of magnesium chloride, 95 mL of methylbenzene, 4 mL of epoxy chloropropane, and 12.5 mL of tributyl phosphate (TBP) were placed one by one into a reactor replaced by high-purity nitrogen. The obtained mixture was stirred and heated to be kept at 50° C. for 2.5 hours. After a complete dissolution of the solid, 1.4 g of phthalic anhydride was added to the obtained solution. The solution was kept for 1 hour, cooled to a temperature below −25° C., added with TiCl 4 within 1 hour, and slowly heated to 80° C. to gradually precipitate the solid. Then, DNBP (di-n-butyl phthalate; 0.003 mol) and 2,6-diisopropyl-N-butylidene aniline of the Formula I (0.003 mol) were added. The obtained mixture was kept for 1 hour, then filtered thermally, added with 150 mL of methylbenzene, and washed twice to obtain a solid. The mixture was added with 100 mL of methylbenzene, stirred for 30 minutes, heated to 110° C., washed for three times with each time lasting for 10 minutes, again added with 60 mL of hexane, and washed twice to obtain a solid (catalyst component) of 7.9 g, containing 3.3% Ti, 23.6% Mg and 50.4% Cl.
(2) Polymerization of Propylene
[0099] 2.5 mL of AlEt 3 , and 5 mL of cyclohexyl methyl dimethoxy silane (CHMMS) enabling Al/Si (mol)=25 were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 10 mg of the above prepared solid component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, pressure releasing, and discharging, so that a PP resin could be obtained. See Table 1 for specific data.
Example 2
[0100] Steps of example 2 were the same as those of example 1, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with 2,6-diisopropyl-N-(2-phenylethylidene)aniline. The catalyst component prepared in the present example was used for polymerization. See Table 1 for specific data.
Example 3
[0101] Steps of example 3 were the same as those of example 1, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with 2,6-dimethyl-N-(2,2-diphenylethylidene) aniline. The catalyst component prepared in the present example was used for polymerization. See Table 1 for specific data.
Example 4
[0102] Steps of example 4 were the same as those of example 1, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with N-(2-phenylethylidene)-8-aminoquinoline. The catalyst component prepared in the present example was used for polymerization. See Table 1 for specific data.
Example 5
[0103] Steps of example 5 were the same as those of example 1, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with 2,6-dimethyl-N-butylidene aniline. The catalyst component prepared in the present example was used for polymerization. See Table 1 for specific data.
Example 6
[0104] Steps of example 6 were the same as those of example 1, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with 2,6-diisopropyl-N-(2,2-diphenylethylidene) aniline. The catalyst component prepared in the present example was used for polymerization. See Table 1 for specific data.
Example 7
[0105] Steps of example 7 were the same as those of example 1, except that the compound DNBP was substituted with 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. The catalyst component prepared in the present example was used for polymerization. See Table 1 for specific data.
Example 8
[0106] Steps of example 8 were the same as those of example 1, except that the compound DNBP was substituted with diethyl 2,3-dibutylsuccinate. The catalyst component prepared in the present example was used for polymerization. See Table 1 for specific data.
Example 9
[0107] Steps of example 9 were the same as those of example 1, except that the compound DNBP was substituted with 3,5-dibenzoyloxyheptane. The catalyst component prepared in the present example was used for polymerization. See Table 1 for specific data.
Example 10
[0108] Steps of example 10 were the same as those of example 1, except that the amount of the added compound 2,6-diisopropyl-N-butylidene aniline was changed to 0.006 mol. The catalyst component prepared in the present example was used for polymerization. See Table 1 for specific data.
Example 11
[0109] Steps of example 11 were the same as those of example 1, except that the amount of the added compound 2,6-diisopropyl-N-butylidene aniline was changed to 0.0015 mol. The catalyst component prepared in the present example was used for polymerization. See Table 1 for specific data.
Example 12
[0110] Steps of example 12 were the same as those of example 1, except that the time of the polymerization reaction was extended to 2 hours. See Table 1 for specific data.
Example 13
[0111] Steps of example 13 were the same as those of example 1, except that the time of the polymerization reaction was extended to 3 hours. See Table 1 for specific data.
Example 14
[0112] Steps of example 14 were the same as those of example 5, except that the time of the polymerization reaction was extended to 2 hours. See Table 1 for specific data.
Example 15
[0113] Steps of example 15 were the same as those of example 5, except that the time of the polymerization reaction was extended to 3 hours. See Table 1 for specific data.
Example 16
[0114] Steps of example 16 were the same as those of example 1, except that the amount of the added hydrogen gas was changed to 7.2 NL. See Table 1 for specific data.
Comparative Example 1
[0115] Steps of comparative example 1 were the same as those of example 1, except that the no 2,6-diisopropyl-N-butylidene aniline was added, and that the amount of the added DNBP was 0.006 mol. See Table 1 for specific data.
Comparative Example 2
[0116] Steps of comparative example 2 were the same as those of comparative example 1, except that DNBP was substituted with 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (0.006 mol). See Table 1 for specific data.
Comparative Example 3
[0117] Steps of comparative example 3 were the same as those of comparative example 1, except that the amount of the added hydrogen was changed from 1.2 NL to 7.2 NL. See Table 1 for specific data.
[0000]
TABLE 1
Catalyst Activity
Polymer
Melt Index
(Kg polymer/
Isotacticity
M.I
g catalyst)
(%)
(g/10 min)
M w /M n
Example 1
36.5
97.1
3.0
6.9
Example 2
41.6
97.2
3.2
7.0
Example 3
40.5
97.3
3.3
7.1
Example 4
40.2
97.0
3.3
7.0
Example 5
41.9
97.3
3.1
7.0
Example 6
40.3
97.1
3.3
7.2
Comparative
32.5
98.0
1.2
3.8
Example 1
Example 8
39.6
97.6
2.5
6.3
Example 10
38.8
96.6
3.7
7.8
Example 11
34.3
97.7
2.1
5.8
Example 12
64.6
97.6
2.7
6.4
Example 13
85.3
97.7
3.0
7.0
Example 14
68.2
97.8
2.0
6.2
Example 15
89.2
97.6
1.7
—
Example 16
53.2
95.4
36.5
7.5
Comparative
43.8
96.3
28.6
—
Example 3
Example 9
48.5
97.2
3.5
7.4
Example 7
40.2
97.4
2.7
6.4
Comparative
39.3
97.8
7.2
5.5
Example 2
[0118] As can be seen from Table 1, the catalyst provided by the present invention can widen the molecular weight distribution of the obtained polymer. Meanwhile, the catalyst has a relatively high catalytic activity and a good orientation ability, and the polymer obtained has a high isotacticity. This means that the polymer has a good mechanic property and processability. It can be seen from examples 12 to 15 that the catalyst provided by the present invention decreases slowly in activity, and has a relatively high long-term stability. It can be seen from example 16 and comparative example 3 that the catalyst provided by the present invention also has a good hydrogen response. Besides, specifically, with the amounts of internal electron donors being the same, compared with the use of only dicarboxylic ester (e.g., in comparative example 1), the use of the imine compound used in the present invention together with the dicarboxylic ester (examples 1 to 6) can not only greatly improve the activity and isotacticity of the polymerization, but also enable the polymer to have a higher isotacticity and melt index. With the amounts of internal electron donors being the same, compared with the use of only diether (e.g., in comparative example 2), the use of the imine compound used in the present invention together with the diether (example 7) can widen the molecular weight distribution of the polymer and increase catalytic activity. Meanwhile, the catalyst still has a good orientation ability, and the polymer obtained has a relatively high isotacticity.
Group II
Examples and Comparative Examples
Example 1
(1) Preparation of a Solid Catalyst Component
[0119] 36.5 mL of anhydrous ethanol and 21.3 g of anhydrous magnesium chloride were placed into a 250 mL reactor provided therein with a reflux condenser, a mechanical agitator, and a thermometer, and fully replaced by nitrogen. The mixture was stirred and heated to lead to a complete dissolution of magnesium chloride, then added with 75 mL of white oil and 75 mL of silicone oil, and kept at 120° C. for a certain time. 112.5 mL of white oil and 112.5 mL of silicone oil were added in advance in a second 500 mL reactor provided therein with a homogenizer, and preheated to 120° C. The previous mixture was pressed rapidly into the second reactor. The resulting mixture in the second reactor was kept at 120° C. and stirred at a speed of 3500 rmp for 3 minutes, and was transferred to a third reactor while being stirred. The third rector was added with 1600 mL of hexane in advance and was cooled to −25° C. Until finishing transfer of the mixture into the third reactor, the mixture had an ultimate temperature not higher than 0° C. The resulting mixture was subjected to suction filtration, and was washed with hexane and dried in vacuum to obtain spheric particles of an alcohol adduct of magnesium chloride of 41 g. After the obtained particles were screened, carriers (100-400 mesh) were taken for analysis. The analysis showed that the component of the carriers was MgCl 2 .2.38C 2 H 5 OH.
[0120] 7 g of the above MgCl 2 .2.38C 2 H 5 OH spheric carriers was measured and added 5 slowly into a reactor which was provided therein in advance with 100 mL of titanium tetrachloride and pre-cooled to −20° C. The resulting mixture in the reactor were heated gradually to 40° C., followed by addition of 2, 4-dibenzoyloxypentane (0.003 mol) and a compound 2,6-diisopropylbutylidene aniline (0.003 mol) of the Formula IV. The resulting mixture was heated continuously to 100° C. in 1 hour, kept for 2 hours, and then subjected to suction filtration. The mixture was again added with 100 mL of TiCl 4 , then heated to 120° C. in 1 hour, kept for 2 hours, and subjected to suction filtration. After that, the mixture was washed with 60 mL of hexane for several times until the filtrate contained no chloridion. The filter cake was dried in vacuum to obtain a solid catalyst component.
(2) Polymerization of Propylene
[0121] 2.5 mL of AlEt 3 , and 0.1 mmol of cyclohexyl methyl dimethoxy silane (CHMMS) were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 8-10 mg of the above prepared solid catalyst component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, and pressure releasing, so that a PP powder could be obtained. See Table 2 for specific polymerization data.
Example 2
[0122] The steps of the present example were the same as those of example 1 of the present group, except that the amount of the added compound 2,6-diisopropyl-N-butylidene aniline was changed into 6 mmol. See Table 2 for specific data.
Example 3
[0123] The steps of the present example were the same as those of example 1 of the present group, except that the amount of the added compound 2,6-diisopropyl-N-butylidene aniline was changed into 1.5 mmol. See Table 2 for specific data.
Example 4
[0124] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with 2,6-diisopropyl-N-(2-phenylethylidene) aniline. See Table 2 for specific data.
Example 5
[0125] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with 2,6-dimethyl-N-(2,2-diphenylethylidene) aniline. See Table 2 for specific data.
Example 6
[0126] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with N-(2-phenylethylidene)-8-aminoquinoline. See Table 2 for specific data.
Example 7
[0127] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with 2,6-dimethyl-N-butylidene aniline. See Table 2 for specific polymerization data.
Example 8
[0128] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with 2,6-diisopropyl-N-(2,2-diphenylethylidene) aniline. See Table 2 for specific data.
Example 9
[0129] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2,4-dibenzoyloxy pentane was substituted with 3,5-dibenzoyloxy heptane. See Table 2 for specific data.
Example 10
[0130] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2,4-dibenzoyloxy pentane was substituted with 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. See Table 2 for specific polymerization data.
Example 11
[0131] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2, 4-dibenzoyloxy pentane was substituted with diethyl 2,3-dibutylsuccinate. See Table 2 for specific data.
Example 12
[0132] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2, 4-dibenzoyloxy pentane was substituted with di-n-butyl phthalate (DNBP). See Table 2 for specific data.
Example 13
(1) Preparation of a Solid Catalyst Component
[0133] 36.5 mL of anhydrous ethanol and 21.3 g of anhydrous magnesium chloride were placed into a 250 mL reactor provided therein with a reflux condenser, a mechanical agitator, and a thermometer, and replaced by nitrogen gas. The mixture was stirred and heated to lead to a complete dissolution of magnesium chloride, then added with 75 mL of white oil and 75 mL of silicone oil, and kept at 120° C. for a certain time. 112.5 mL of white oil and 112.5 mL of silicone oil were added in advance in a second 500 mL reactor provided therein with a homogenizer, and preheated to 120° C. The previous mixture was pressed rapidly into the second reactor. The resulting mixture in the second reactor was kept at 120° C. and stirred at a speed of 3500 rmp for 3 minutes, and was transferred to a third reactor while being stirred. The third rector was added with 1600 mL of hexane in advance and was cooled to −25° C. Until finishing transfer of the mixture into the third reactor, the mixture had an ultimate temperature not higher than 0° C. The resulting mixture was subjected to suction filtration, and was washed with hexane and dried in vacuum to obtain spheric particles of an alcohol adduct of magnesium chloride of 41 g. After the obtained particles were screened, carriers (100-400 mesh) were taken for analysis. The analysis showed that the component of the carriers was MgCl 2 2.38C 2 H 5 OH.
[0134] 7 g of the above MgCl 2 .2.38C 2 H 5 OH spheric carriers was measured and added slowly into a reactor which was provided therein in advance with 100 mL of titanium tetrachloride and pre-cooled to −20° C. The resulting mixture in the reactor was heated gradually to 40° C., followed by addition of 2, 4-dibenzoyloxypentane (0.006 mol). The resulting mixture was heated continuously to 100° C. in 1 hour, kept for 2 hours, and then subjected to suction filtration. The mixture was again added with 100 mL of TiCl 4 , then heated to 120° C. in 1 hour, kept for 2 hours, and subjected to suction filtration. After that, the mixture was added with 60 mL of hexane and the compound 2,6-diisopropyl-N-butylidene aniline of said structure (0.006 mol), and stirred for 30 minutes. The resulting mixture was washed with 60 mL of hexane for several times until the filtrate contained no chloridion. The filter cake was dried in vacuum to obtain a solid catalyst component.
(2) Polymerization of Propylene
[0135] 2.5 mL of AlEt 3 , and 0.1 mmol of cyclohexyl methyl dimethoxy silane (CHMMS) were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 8-10 mg of the above prepared solid catalyst component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, and pressure releasing, so that a PP powder could be obtained. See Table 2 for specific polymerization data.
Example 14
[0136] The steps of the present example were the same as those of example 1 of the present group, except that the time of the polymerization reaction was extend to 2 hours. See Table 2 for the results.
Example 15
[0137] The steps of the present example were the same as those of example 1 of the present group, except that the time of the polymerization reaction was extend to 3 hours. See Table 2 for the results.
Example 16
[0138] The steps of the present example were the same as those of example 7 of the present group, except that the time of the polymerization reaction was extend to 2 hours. See Table 2 for the results.
Example 17
[0139] The steps of the present example were the same as those of example 7 of the present group, except that the time of the polymerization reaction was extend to 3 hours. See Table 2 for the results.
Example 18
[0140] The steps of the present example were the same as those of example 1 of the present group, except that the amount of the added hydrogen gas was changed to 7.2 NL. See Table 2 for the results.
Comparative Example 1
[0141] Steps of comparative example 1 were the same as those of example 1 of the present group, except that the no imine compound (2,6-diisopropyl-N-butylidene aniline) was added, and that the amount of the added 2, 4-dibenzoyloxy pentane was 0.006 mol. See Table 2 for specific polymerization data.
[0000]
TABLE 2
Catalyst Activity
Polymer
Melt Index
(Kg polymer/
Isotacticity
M.I
g catalyst)
(%)
(g/10 min)
Mw/Mn
Example 1
48.0
97.7
3.0
8.3
Example 2
40.6
97.4
3.7
8.9
Example 3
43.2
97.5
3.0
7.9
Example 4
39.7
97.2
3.1
8.0
Example 5
46.5
97.6
3.3
8.7
Example 6
45.2
97.6
3.4
8.9
Example 7
43.9
97.7
3.1
8.4
Example 8
50.3
97.4
3.3
8.7
Comparative
46.6
96.5
3.6
6.9
Example 1
Example 9
48.7
96.5
4.6
8.9
Example 10
37.2
97.4
6.6
7.0
Example 11
39.6
97.6
3.5
8.8
Example 12
38.5
97.8
3.1
7.9
Example 13
40.7
97.7
3.1
8.5
Example 14
65.6
97.7
3.1
—
Example 15
87.3
97.7
3.0
—
Example 16
68.7
97.8
3.2
—
Example 17
91.2
97.6
3.0
—
Example 18
59.2
95.4
46.5
—
[0142] As can be seen from Table 2, the catalyst provided by the present invention can widen the molecular weight distribution of the obtained polymer. Meanwhile, the obtained catalyst has a high catalytic activity and a good orientation ability, and the polymer obtained has a high isotacticity and a suitable melt index. This means that the polymer has a good mechanic property, flowing property, and processability. Besides, it can be seen from examples 14 to 17 that the obtained catalyst decreases slowly in activity, and has a higher long-term stability. It can be seen from example 18 that the catalyst provided by the present invention also has a good hydrogen response. Specifically, with the amounts of internal electron donors being the same, compared with the use of only one internal electron donor (in comparative example), the use of the imine compound used in the present invention together with the one internal electron donor (examples 1 to 8) can not only cause the polymer to have a higher isotacticity and a wider molecular weight distribution, but also enable the catalyst to have a higher catalytic activity and a better orientation capability.
Group III
Examples and Comparative Examples
Example 1
[0143] Under a nitrogen atmosphere, 4.8 g of anhydrous magnesium chloride, 19.5 g of isooctanol, and 19.5 g of decane were placed into a 500 mL reactor provided therein with an agitator, then heated to 130° C. to react for 1.5 hours until a complete dissolution of magnesium chloride. After an addition of 1.1 g phthalic anhydride, the mixture was kept at 130° C. to react for 1 hour to obtain an alcohol adduct of magnesium chloride, which was then cooled to room temperature. Under a nitrogen atmosphere, the above alcohol adduct was added into 120 mL of titanium tetrachloride solution which was precooled to −22° C. The resulting mixture was heated slowly to 100° C., and added with DNBP (di-n-butyl phthalate; 0.003 mol) and a compound 2,6-diisopropyl-N-butylidene aniline (0.003 mol). The mixture was heated and kept at 110° C. for 2 hours, followed by an immediate filtration. The mixture was then added with 120 mL of titanium tetrachloride solution, heated to 110° C. to react for 1 hour, and filtered. The resulting mixture was added with 80 mL of methylbenzene, 2.66 g of tributyl phosphate, and kept at 90° C. for 0.5 hour. Solid particles were washed with anhydrous hexane for four times, and dried to obtain a solid catalyst component.
[0144] 2.5 mL of AlEt 3 , and 0.1 mmol of cyclohexyl methyl dimethoxy silane (CHMMS) were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 8-10 mg of the above prepared solid catalyst component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, and pressure releasing, so that a PP powder could be obtained. See Table 3 for specific polymerization data.
Example 2
[0145] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with 2,6-diisopropyl-N-(2-phenylethylidene) aniline. See Table 3 for specific data.
Example 3
[0146] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with 2,6-dimethyl-N-(2,2-diphenylethylidene) aniline. See Table 3 for specific data.
Example 4
[0147] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with N-(2-phenylethylidene)-8-aminoquinoline. See Table 3 for specific data.
Example 5
[0148] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with 2,6-dimethyl-N-butylidene aniline. See Table 3 for specific data.
Example 6
[0149] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2,6-diisopropyl-N-butylidene aniline was substituted with 2,6-diisopropyl-N-(2,2-diphenylethylidene) aniline. See Table 3 for specific data.
Example 9
[0150] The steps of the present example were the same as those of example 1 of the present group, except that the compound DNBP was substituted with 2, 4-dibenzoyloxy pentane. See Table 3 for specific data.
Example 10
[0151] The steps of the present example were the same as those of example 1 of the present group, except that the compound DNBP was substituted with 2-isopropyl-2-isopentyl-1,3-dimethoxy propane. See Table 3 for specific data.
Example 11
[0152] The steps of the present example were the same as those of example 1 of the present group, except that the compound DNBP was substituted with diethyl 2,3-dibutyl succinate. See Table 3 for specific data.
Example 12
[0153] The steps of the present example were the same as those of example 1 of the present group, except that the compound DNBP was substituted with 3,5-benzoyloxy heptane. See Table 3 for specific data.
Example 13
[0154] Under a nitrogen atmosphere, 4.8 g of anhydrous magnesium chloride, 19.5 g of isooctanol, and 19.5 g of decane were placed into a 500 mL reactor provided therein with an agitator, then heated to 130° C. to react for 1.5 hours until a complete dissolution of magnesium chloride. After an addition of 1.1 g phthalic anhydride, the mixture was kept at 130° C. to react for 1 hour to obtain an alcohol adduct of magnesium chloride, which was then cooled to room temperature. Under a nitrogen atmosphere, the above alcohol adduct was added into 120 mL of titanium tetrachloride solution which was precooled to −22° C. The resulting mixture was heated slowly to 100° C., and added with 2, 4-dibenzoyloxypentane (0.006 mol). The mixture was heated and kept at 110° C. for 2 hours, followed by an immediate filtration. The mixture was again added with 120 mL of titanium tetrachloride solution, heated to 110° C. to react for 1 hour, and filtered. The resulting mixture was added with 80 mL of methylbenzene, and a compound 2,6-diisopropyl-N-butylidene aniline (0.006 mol) with said structure, and kept at 90° C. for 0.5 hour. Solid particles were washed with anhydrous hexane for four times, and dried to obtain a solid catalyst component.
[0155] 2.5 mL of AlEt 3 , and 0.1 mmol of cyclohexyl methyl dimethoxy silane (CHMMS) were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 8-10 mg of the above prepared solid catalyst component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, and pressure releasing, so that a PP powder could be obtained. See Table 3 for specific polymerization data.
Example 14
[0156] The steps of the present example were the same as those of example 1 of the present group, except that the time of the polymerization reaction was extend to 2 hours. See Table 3 for the results.
Example 15
[0157] The steps of the present example were the same as those of example 1 of the present group, except that the time of the polymerization reaction was extend to 3 hours. See Table 3 for the results.
Example 16
[0158] The steps of the present example were the same as those of example 5 of the present group, except that the time of the polymerization reaction was extend to 2 hours. See Table 3 for the results.
Example 17
[0159] The steps of the present example were the same as those of example 5 of the present group, except that the time of the polymerization reaction was extend to 3 hours. See Table 3 for the results.
Example 18
[0160] The steps of the present example were the same as those of example 1 of the present group, except that the amount of the added hydrogen gas was changed to 7.2 NL. See Table 3 for the results.
Comparative Example 1
[0161] Steps of comparative example 1 were the same as those of example 1 of the present group, except that the no 2,6-diisopropyl-N-butylidene aniline was added, and that the amount of the added DNBP was 0.006 mol. See Table 3 for specific polymerization data.
[0000]
TABLE 3
Catalyst Activity
Polymer
Melt Index
(Kg polymer/
Isotacticity
M.I
g catalyst)
(%)
(g/10 min)
M w /M n
Example 1
37.6
97.2
3.1
7.0
Example 2
42.7
97.3
3.2
7.2
Example 3
41.4
97.3
3.3
7.5
Example 4
40.8
97.1
3.4
7.8
Example 5
40.9
97.5
3.1
7.1
Example 6
41.0
97.2
3.3
7.5
Comparative
45.1
96.7
3.0
5.6
Example 1
Example 7
39.8
97.4
3.9
8.0
Example 8
37.0
97.1
3.1
6.6
Example 9
42.3
97.7
3.8
7.8
Example 10
41.5
97.5
6.2
6.5
Example 11
39.8
97.7
3.5
8.4
Example 12
38.8
97.3
3.5
8.0
Example 13
43.0
97.7
3.1
8.1
Example 14
65.2
97.7
3.7
nd
Example 15
88.1
97.8
3.0
nd
Example 16
72.4
97.8
3.1
nd
Example 17
91.2
97.7
3.1
nd
Example 18
53.2
95.4
41.0
nd
[0162] As can be seen from Table 3, the catalyst provided by the present invention can widen the molecular weight distribution, improve isotacticity, and has a good orientation ability. Meanwhile, the obtained catalyst has a high catalytic activity, and the polymer obtained has a relatively high melt index. This means that the polymer has a good mechanic property, flowing property, and processability. Specifically, compared with the use of only one compound B (e.g., dicarboxylic ester compound as internal electron donor in comparative example 1) as the internal electron donor, the use of the compound of Formula I of the present invention and the compound B (examples 1 to 6) as internal electron donors can widen the molecular weight distribution, and improve the isotacticity of the polymer and the orientation ability of the catalyst. Meanwhile, the catalyst provided by the present invention also has a high catalytic activity, and the obtained polymer has a high melt index. Besides, it can be seen from examples 14 to 17 that the obtained catalyst decreases more slowly in activity, and hence has a higher long-term stability. It can be seen from example 18 that the catalyst provided by the present invention has a good hydrogen response.
Group IV
Examples and Comparative Examples
Example 1
(1) Preparation of a Catalyst Component
[0163] 4.8 g of magnesium chloride, 95 mL of methylbenzene, 4 mL of epoxy chloropropane, and 12.5 mL of tributyl phosphate (TBP) were placed one by one into a reactor replaced by high-purity nitrogen. The obtained mixture was stirred and heated to be kept at 50° C. for 2.5 hours. After a complete dissolution of the solid, 1.4 g of phthalic anhydride was added to the obtained solution. The solution was kept for 1 hour, cooled to a temperature below −25° C., added with TiCl 4 within 1 hour, and slowly heated to 80° C. to gradually precipitate a solid. Then, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane of the Formula IV as an electron donor (0.006 mol) was added. The obtained mixture was kept for 1 hour, then filtered thermally, added with 150 mL of methylbenzene, and washed twice to obtain a solid. The mixture was added with 100 mL of methylbenzene, heated to 110° C., washed for three times with each time lasting for 10 minutes. The mixture was again added with 2-(2,6-diisopropylphenylimino)methyl-4,6-di-tert-butylphenol of the Formula II as an electron donor (0.006 mol) and 60 mL of hexane, stirred for 30 minutes, and was again added with 60 mL of hexane, washed for three times to obtain a solid (catalyst component) of 7.4 g, containing 3.6% Ti, 23.2% Mg, and 50.7% Cl.
(2) Polymerization of Propylene
[0164] 2.5 mL of AlEt 3 , and 5 mL of cyclohexyl methyl dimethoxy silane enabling Al/Si (mol)=25 were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 10 mg of the above prepared solid component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, pressure releasing, and discharging, so that a PP resin could be obtained. See Table 4 for specific data.
Example 2
[0165] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2-isopropyl-2-isopentyl-1,3-dimethoxypropane as the electron donor was substituted with 9,9-dimethoxymethylfluorene. See Table 4 for specific data.
Example 3
(1) Preparation of a Catalyst Component
[0166] 4.8 g of magnesium chloride, 95 mL of methylbenzene, 4 mL of epoxy chloropropane, and 12.5 mL of tributyl phosphate (TBP) were placed one by one into a reactor replaced by high-purity nitrogen. The obtained mixture was stirred and heated to be kept at 50° C. for 2.5 hours. After a complete dissolution of the solid, 1.4 g of phthalic anhydride was added to the obtained solution. The solution was kept for 1 hour, cooled to a temperature below −25° C., added with TiCl 4 within 1 hour, and slowly heated to 80° C. to gradually precipitate a solid. Then, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane of the Formula IV as an electron donor (0.003 mol), and 2-(8-quinolylimino)methyl-4,6-di-tert-butylphenol of the Formula II as an electron donor (0.003 mol) were added. The resulting mixture was kept for 1 hour, then filtered thermally, added with 150 mL of methylbenzene, and washed twice obtain a solid. The mixture was added with 100 mL of methylbenzene, stirred for 30 minutes, heated to 110° C., and washed for three times with each time lasting for 10 minutes. The mixture was again added 60 mL of hexane, and washed for three times to obtain a solid (catalyst component) of 6.9 g, containing 3.3% Ti, 22.5% Mg, and 51.6% Cl.
(2) Polymerization of Propylene
[0167] 2.5 mL of AlEt 3 , and 5 mL of cyclohexyl methyl dimethoxy silane enabling Al/Si (mol)=25 were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 10 mg of the above prepared solid component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, pressure releasing, and discharging, so that a PP resin could be obtained. See Table 4 for specific data.
Example 4
[0168] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol as the electron donor was substituted with 2-(2,6-diisopropylphenylimino)methyl-4,6-di-tert-butylphenol. See Table 4 for specific data.
Example 5
[0169] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol as the electron donor was substituted with 2-(2,6-diisopropylphenylimino)methyl-4-tert-butylphenol. See Table 4 for specific data.
Example 6
[0170] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol as the electron donor was substituted with 2-(3-quinolylimino)methyl-4,6-di-tert-butylphenol. See Table 4 for specific data.
Example 7
[0171] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol as the electron donor was substituted with 2-(p-bromophenylimino)methyl-4,6-di-tert-butylphenol. See Table 4 for specific data.
Example 8
[0172] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol as the electron donor was substituted with N-(1-naphthylmethylene)-2,6-diisopropyl aniline. See Table 4 for specific data.
Example 9
[0173] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-isopropyl-2-isopentyl-1,3-dimethoxy propane as the electron donor was substituted with 9,9-dimethoxymethylfluorene. See Table 4 for specific data.
Example 10
(1) Preparation of a Catalyst Component
[0174] 300 mL of TiCl 4 was placed into a reactor replaced by high-purity nitrogen, cooled to −20° C., and was added with 7 g of alcohol adduct of magnesium chloride (see patent CN1330086A). The resulting mixture was stirred and heated in stages. When the mixture was heated to 40° C., the compound 2-isopropyl-2-isopentyl-1,3-dimethoxy propane of the Formula IV (0.003 mol), and the compound 2-(2,6-diisopropylphenylimino)methyl-4,6-di-tert-butylphenol (0.003 mol) as electron donors were added. The resulting mixture was kept for 2 hours, filtered, added with 100 mL of TiCl 4 , heated to 110° C., and treated for three times. After that, the mixture was added with 60 mL of hexane, and washed for three times to obtain a solid (catalyst component) of 7.1 g, containing 3.7% Ti, 23.6% Mg, and 51.0% Cl.
(2) Polymerization of Propylene
[0175] 2.5 mL of AlEt 3 , and 5 mL of cyclohexyl methyl dimethoxy silane enabling Al/Si (mol)=25 were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 10 mg of the above prepared solid component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, pressure releasing, and discharging, so that a PP resin could be obtained. See Table 4 for specific data.
Example 11
(1) Preparation of a Catalyst Component
[0176] 300 mL of TiCl 4 was placed into a reactor replaced by high-purity nitrogen, cooled to −20° C., and was added with 7 g of magnesium ethylate carriers. The resulting mixture was stirred and heated in stages. When the mixture was heated to 40° C., the compound 2-isopropyl-2-isopentyl-1,3-dimethoxy propane of the Formula IV (0.003 mol), and the compound 2-(3-quinolylimino)methyl-4,6-di-tert-butylphenol (0.003 mol) as electron donors were added. The resulting mixture was kept for 2 hours, filtered, added with 100 mL of TiCl 4 , heated to 110° C., and treated for three times. After that, the mixture was added with 60 mL of hexane, and washed for three times to obtain a solid (catalyst component) of 6.7 g, containing 3.4% Ti, 22.6% Mg, and 49.6% Cl.
(2) Polymerization of Propylene
[0177] 2.5 mL of AlEt 3 , and 5 mL of cyclohexyl methyl dimethoxy silane enabling Al/Si (mol)=25 were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 10 mg of the above prepared solid component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, pressure releasing, and discharging, so that a PP resin could be obtained. See Table 4 for specific data.
Example 12
[0178] The steps of the present example were the same as those of example 1 of the present group, except that the time of the polymerization reaction was extend to 2 hours. See Table 4 for the results.
Example 13
[0179] The steps of the present example were the same as those of example 1 of the present group, except that the time of the polymerization reaction was extend to 3 hours. See Table 4 for the results.
Example 14
[0180] The steps of the present example were the same as those of example 4 of the present group, except that the time of the polymerization reaction was extend to 2 hours. See Table 4 for the results.
Example 15
[0181] The steps of the present example were the same as those of example 4 of the present group, except that the time of the polymerization reaction was extend to 3 hours. See Table 4 for the results.
Example 16
[0182] The steps of the present example were the same as those of example 4 of the present group, except that the amount of the added hydrogen gas was changed to 7.2 NL. See Table 4 for the results.
Example 17
[0183] The steps of the present example were the same as those of example 3 of the present group, except that the amount of the added compound 2-(8-quinolylimino)methyl-4,6-di-tert-butylphenol was changed to 0.006 mol. See Table 4 for the results.
Example 18
[0184] The steps of the present example were the same as those of example 3 of the present group, except that the amount of the added compound 2-(8-quinolylimino)methyl-4,6-di-tert-butylphenol was changed to 0.0015 mol. See Table 4 for the results.
Comparative Example 1
[0185] Steps of comparative example 1 were the same as those of example 3 of the present group, except that the no 2-(8-quinolylimino)methyl-4,6-di-tert-butylphenol was added, and that the amount of the added 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was 0.006 mol. See Table 4 for specific data.
[0000]
TABLE 4
Catalyst Activity
Polymer
Melt Index
(Kg polymer/
Isotacticity
M.I
g catalyst)
(%)
(g/10 min)
M w /M n
Example 1
37.5
97.6
8.0
6.4
Example 2
43.8
97.9
8.1
6.4
Example 3
41.5
97.7
8.1
6.5
Example 4
39.0
97.8
8.0
6.6
Example 5
38.6
97.6
8.1
6.8
Example 6
38.3
97.7
8.2
6.5
Example 7
34.6
97.6
8.2
6.6
Example 8
38.3
98.1
6.6
6.6
Example 9
34.3
98.0
8.3
5.6
Example 10
38.1
97.9
8.4
6.2
Example 11
40.6
97.9
8.3
6.8
Example 12
72.7
97.9
7.9
—
Example 13
98.5
97.6
8.0
—
Example 14
71.5
98.0
8.1
—
Example 15
98.9
98.1
8.2
—
Example 16
45.1
97.4
98.3
—
Example 17
42.0
97.6
8.8
6.9
Example 18
43.7
97.8
8.0
6.5
Comparative
39.3
97.8
7.2
5.5
Example 1
[0186] As can be seen from Table 4, the catalyst provided by the present invention can widen the molecular weight distribution, and improve isotacticity, and has a good orientation ability. Meanwhile, the obtained catalyst has a high catalytic activity, and the polymer obtained has a high melt index and isotacticity. This means that the polymer obtained has a good mechanic property, flowing property, and processability. Specifically, compared with the use of only one compound B (e.g., diether compound as internal electron donors in comparative example 1) as the internal electron donor, the use of the compound of Formula II of the present invention and the one compound B (examples 1 to 8) as internal electron donors can widen the molecular weight distribution, improve isotacticity of the polymer and enhance the orientation ability of the catalyst. Meanwhile, the catalyst provided by the present invention also has a high catalytic activity, and the polymer has a high melt index. Besides, it can be seen from examples 12 to 15 that the obtained catalyst decreases more slowly in activity, and hence has a higher long-term stability. It can be seen from example 16 that the catalyst provided by the present invention has a good hydrogen response.
Group V
Examples and Comparative Examples
Example 1
(1) Preparation of a Catalyst Component
[0187] 4.8 g of magnesium chloride, 95 mL of methylbenzene, 4 mL of epoxy chloropropane, and 12.5 mL of tributyl phosphate (TBP) were placed one by one into a reactor replaced by high-purity nitrogen. The obtained mixture was stirred and heated to be kept at 50° C. for 2.5 hours. After a complete dissolution of the solid, 1.4 g of phthalic anhydride was added to the obtained solution. The solution was kept for 1 hour, cooled to a temperature below −25° C., added with TiCl 4 within 1 hour, and slowly heated to 80° C. to gradually precipitate a solid. Then, 2, 4-dibenzoyloxypentane of the Formula III as an electron donor (0.006 mol) was added. The obtained mixture was kept for 1 hour, then filtered thermally, added with 150 mL of methylbenzene, and washed twice to obtain a solid. The mixture was added with 100 mL of methylbenzene, heated to 110° C., washed for three times with each time lasting for 10 minutes. The mixture was again added with 2-(2,6-diisopropylphenylimino)methyl-4,6-di-tert-butylphenol of the Formula II (0.006 mol) and 60 mL of hexane, stirred for 30 minutes, and was again added with 60 mL of hexane, washed for three times to obtain a solid (catalyst component) of 7.4 g, containing 3.8% Ti, 24.2% Mg, and 50.6% Cl.
(2) Polymerization of Propylene
[0188] 2.5 mL of AlEt 3 , and 5 mL of cyclohexyl methyl dimethoxy silane enabling Al/Si (mol)=25 were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 10 mg of the above prepared solid component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, pressure releasing, and discharging, so that a PP resin could be obtained. See Table 5 for specific data.
Example 2
[0189] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2, 4-dibenzoyloxypentane as the electron donor was substituted with 3,5-dibenzoyloxy heptane. See Table 5 for specific data.
Example 3
(1) Preparation of a Catalyst Component
[0190] 4.8 g of magnesium chloride, 95 mL of methylbenzene, 4 mL of epoxy chloropropane, and 12.5 mL of tributyl phosphate (TBP) were placed one by one into a reactor replaced by high-purity nitrogen. The obtained mixture was stirred and heated to be kept at 50° C. for 2.5 hours. After a complete dissolution of the solid, 1.4 g of phthalic anhydride was added to the obtained solution. The solution was kept for 1 hour, cooled to a temperature below −25° C., added with TiCl 4 within 1 hour, and slowly heated to 80° C. to gradually precipitate the solid substance. Then, a compound 2, 4-dibenzoyloxypentane of the Formula III as a electron donor (0.003 mol), and a compound 2-(8-quinolylimino)methyl-4,6-di-tert-butylphenol of the Formula II as an electron donor (0.003 mol) were added. The resulting mixture was kept for 1 hour, then filtered thermally, added with 150 mL of methylbenzene, and washed twice to obtain a solid. The mixture was added with 100 mL of methylbenzene, stirred for 30 minutes, heated to 110° C., and washed for three times with each time lasting for 10 minutes. The mixture was again added with 60 mL of hexane, and washed for three times to obtain a solid (catalyst component) of 6.9 g, containing 3.5% Ti, 23.5% Mg, and 52.0% Cl.
(2) Polymerization of Propylene
[0191] 2.5 mL of AlEt 3 , and 5 mL of cyclohexyl methyl dimethoxy silane enabling Al/Si (mol)=25 were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 10 mg of the above prepared solid component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, pressure releasing, and discharging, so that a PP resin could be obtained. See Table 5 for specific data.
Example 4
[0192] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol as the electron donor was substituted with 2-(2,6-diisopropylphenylimino)methyl-4,6-di-tert-butylphenol. See Table 5 for specific data.
Example 5
[0193] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol as the electron donor was substituted with 2-(2,6-diisopropylphenylimino)methyl-4-tert-butylphenol. See Table 5 for specific data.
Example 6
[0194] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol as the electron donor was substituted with 2-(2,6-dimethylphenylimino)methyl-4-tert-butylphenol. See Table 5 for specific data.
Example 7
[0195] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol as the electron donor was substituted with 2-(3-quinolylimino)methyl-4,6-di-tert-butyl phenol. See Table 5 for specific data.
Example 8
[0196] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol as the electron donor was substituted with 2-(4-quinolylimino)methyl-4,6-di-tert-butyl phenol. See Table 5 for specific data.
Example 9
[0197] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol as the electron donor was substituted with 2-(p-bromophenylimino)methyl-4,6-di-tert-butylphenol. See Table 5 for specific data.
Example 10
[0198] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol as the electron donor was substituted with N-(1-naphthylmethylene)-2,6-diisopropyl aniline. See Table 5 for specific data.
Example 11
(1) Preparation of a Catalyst Component
[0199] 300 mL of TiCl 4 was placed into a reactor replaced by high-purity nitrogen, cooled to −20° C., and was added with 7 g of alcohol adduct of magnesium chloride (see patent CN1330086A). The resulting mixture was stirred, and heated in stages. When the mixture was heated to 40° C., the compound 2, 4-dibenzoyloxypentane of the Formula III (0.003 mol), and the compound 2-(2,6-diisopropylphenylimino)methyl-4,6-di-tert-butylphenol of the Formula II (0.003 mol) as electron donors were added. The resulting mixture was kept for 2 hours, filtered, added with 100 mL of TiCl 4 , heated to 110° C., and treated for three times. After that, the mixture was added with 60 mL of hexane, and washed for three times to obtain a solid (catalyst component) of 6.7 g, containing 3.7% Ti, 26.6% Mg, and 51.6% Cl.
(2) Polymerization of Propylene
[0200] 2.5 mL of AlEt 3 , and 5 mL of cyclohexyl methyl dimethoxy silane enabling Al/Si (mol)=25 were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 10 mg of the above prepared solid component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, pressure releasing, and discharging, so that a PP resin could be obtained. See Table 5 for specific data.
Example 12
[0201] The steps of the present example were the same as those of example 1 of the present group, except that the time of the polymerization reaction was extend to 2 hours. See Table 5 for the results.
Example 13
[0202] The steps of the present example were the same as those of example 1 of the present group, except that the time of the polymerization reaction was extend to 3 hours. See Table 5 for the results.
Example 14
[0203] The steps of the present example were the same as those of example 7 of the present group, except that the time of the polymerization reaction was extend to 2 hours. See Table 5 for the results.
Example 15
[0204] The steps of the present example were the same as those of example 4 of the present group, except that the amount of the added hydrogen gas was changed to 7.2 NL. See Table 5 for the results.
Example 16
[0205] The steps of the present example were the same as those of example 4 of the present group, except that the time of the polymerization reaction was extend to 2 hours. See Table 5 for the results.
Example 17
[0206] The steps of the present example were the same as those of example 4 of the present group, except that the time of the polymerization reaction was extend to 3 hours. See Table 5 for the results.
Comparative Example 1
[0207] Steps of comparative example 1 were the same as those of example 3 of the present group, except that the no 2-(8-quinolylimino)methyl-4,6-di-tert-butylphenol was added, and that the amount of the added 2, 4-dibenzoyloxy pentane was 0.006 mol. See Table 5 for specific data.
Comparative Example 2
[0208] The steps of comparative example 2 were the same as those of example 1 of the present group, except that the amount of the added hydrogen gas was changed to 7.2 NL. See Table 5 for the results.
[0000]
TABLE 5
Catalyst Activity
Polymer
Melt Index
(Kg polymer/
Isotacticity
M.I
g catalyst)
(%)
(g/10 min)
M w /M n
Example 1
43.5
97.6
1.7
8.2
Example 2
50.2
97.3
1.3
8.1
Example 3
51.5
97.7
1.0
8.0
Example 4
45.0
97.8
1.0
7.8
Example 5
41.6
97.6
1.0
7.9
Example 6
40.5
97.4
0.9
8.0
Example 7
48.6
98.2
0.8
8.0
Example 8
33.5
96.5
1.3
8.2
Example 9
42.3
97.8
1.3
8.2
Example 10
35.7
97.1
0.9
8.1
Example 11
40.1
97.4
6.2
8.4
Example 12
62.7
97.8
1.6
—
Example 13
87.5
97.6
1.3
—
Example 14
76.1
99.1
0.8
—
Example 16
71.5
98.0
1.5
7.7
Example 17
88.9
98.1
1.6
7.6
Comparative
44.3
97.9
2.4
6.9
Example 1
Example 15
56.7
95.6
32.5
—
Comparative
45.7
97.8
20.4
—
Example 2
[0209] As can be seen from Table 5, the catalyst provided by the present invention can widen the molecular weight distribution, improve isotacticity, and has a good orientation ability. Meanwhile, the obtained catalyst has a high catalytic activity, and the polymer obtained has a high melt index and isotacticity. This means that the polymer obtained has a good mechanic property, flowing property, and processability. Specifically, compared with the use of only one compound B (e.g., diol ester compound as internal electron donors in comparative example 1) as the internal electron donor, the use of the compound of Formula II of the present invention and the compound B as internal electron donors (examples 1 to 11) can widen the molecular weight distribution of the polymer. Meanwhile, the catalyst provided by the present invention also has a high catalytic activity, and a good orientation ability, and the polymer has a high melt index and isotacticity. Besides, it can be seen from examples 12 to 14 and 16 to 17 that the obtained catalyst decreases more slowly in activity, and has a higher long-term stability. It can be seen from example 15 and comparative example 2 that the catalyst provided by the present invention has a good hydrogen response.
[0210] It can also be seen from a comparison between the data of comparative examples 1 and 2 and the data of the examples that, when used in propene polymerization reaction, the catalyst provided by the present invention, on the one hand, has a high catalytic activity and a good hydrogen response, and is low in decrease of activity, and on the other hand, can enable the obtained polymer to have a high isotacticity (up to 99.1%; see example 14), a high melt index, and a wider molecular weight distribution, thereby leading to a wide application of the polymer.
Group VI
Examples and Comparative Examples
Example 1
(1) Preparation of a Catalyst Component
[0211] 4.8 g of magnesium chloride, 95 mL of methylbenzene, 4 mL of epoxy chloropropane, and 12.5 mL of tributyl phosphate (TBP) were placed one by one into a reactor replaced by high-purity nitrogen. The obtained mixture was stirred and heated to be kept at 50° C. for 2.5 hours. After a complete dissolution of the solid, 1.4 g of phthalic anhydride was added to the obtained solution. The solution was kept for 1 hour, cooled to a temperature below −25° C., added with TiCl 4 within 1 hour, and slowly heated to 80° C. to gradually precipitate a solid. Then, DNBP (0.006 mol) was added. The obtained mixture was kept for 1 hour, then filtered thermally, added with 150 mL of methylbenzene, and washed twice to obtain a solid. The mixture was added with 100 mL of methylbenzene, heated to 110° C., washed for three times with each time lasting for 10 minutes. The mixture was added with a compound 2-(2,6-dimethylphenylimino)methyl-4,6-di-tert-butylphenol of the Formula II (0.006 mol) and 60 mL of hexane, stirred for 30 minutes, and was again added with 60 mL of hexane, washed for three times to obtain a solid (catalyst component) of 7.4 g, containing 3.8% Ti, 24.2% Mg, and 52.6% Cl.
(2) Polymerization of Propylene
[0212] 2.5 mL of AlEt 3 , and 5 mL of cyclohexyl methyl dimethoxy silane enabling Al/Si (mol)=25 were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 10 mg of the above prepared solid component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, pressure releasing, and discharging, so that a PP resin could be obtained. See Table 6 for specific data.
Example 2
[0213] The steps of the present example were the same as those of example 1 of the present group, except that the compound DNBP was substituted with DIBP (diisobutyl phthalate). See Table 6 for specific data.
Example 3
(1) Preparation of a Catalyst Component
[0214] 4.8 g of magnesium chloride, 95 mL of methylbenzene, 4 mL of epoxy chloropropane, and 12.5 mL of tributyl phosphate (TBP) were placed one by one into a reactor replaced by high-purity nitrogen. The obtained mixture was stirred and heated to be kept at 50° C. for 2.5 hours. After a complete dissolution of the solid, 1.4 g of phthalic anhydride was added to the obtained solution. The solution was kept for 1 hour, cooled to a temperature below −25° C., added with TiCl 4 within 1 hour, and slowly heated to 80° C. to gradually precipitate a solid. Then, DNBP (0.003 mol), and a compound 2-(8-quinolylimino)methyl-4,6-di-tert-butylphenol of the Formula II (0.003 mol) were added. The resulting mixture was kept for 1 hour, then filtered thermally, added with 150 mL of methylbenzene, and washed twice to obtain a solid. The mixture was added with 100 mL of methylbenzene, stirred for 30 minutes, heated to 110° C., and washed for three times with each time lasting for 10 minutes. The mixture was again added with 60 mL of hexane, and washed for three times to obtain a solid (solid catalyst component) of 6.9 g, containing 3.5% Ti, 22.5% Mg, and 51.6% Cl.
[0215] (2) Steps of polymerization of propylene were the same as example 1 of the present group. See Table 6 for specific data.
Example 4
[0216] The steps of the present example were the same as those of example 1 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol was substituted with 2-(2,6-diisopropylphenylimino)methyl-4,6-di-tert-butylphenol. See Table 6 for specific data.
Example 5
[0217] The steps of the present example were the same as those of example 3 of the present group, except that the compound 2-(8-quinolylimino)methyl-4,6-di-tert-butyl phenol was substituted with 2-(3-quinolylimino)methyl-4,6-di-tert-butyl phenol. See Table 6 for specific data.
Example 6
(1) Preparation of a Catalyst Component
[0218] 300 mL of TiCl 4 was placed into a reactor replaced by high-purity nitrogen, cooled to −20° C., and was added with 7 g of an alcohol adduct of magnesium chloride (see patent CN1330086A). The resulting mixture was stirred, and heated in stages. When the mixture was heated to 40° C., the compound DNBP (0.003 mol), and the compound 2-(2,6-diisopropylphenylimino)methyl-4,6-di-tert-butylphenol of the Formula II (0.003 mol) were added. The resulting mixture was kept for 2 hours, filtered, added with 100 mL of TiCl 4 , heated to 110° C., and treated for three times. After that, the mixture was added with 60 mL of hexane, and washed for three times to obtain a solid (solid catalyst component) of 7.1 g, containing 3.5% Ti, 26.6% Mg, and 50.6% Cl.
(2) Polymerization of Propylene
[0219] 2.5 mL of AlEt 3 , and 5 mL of cyclohexyl methyl dimethoxy silane enabling Al/Si (mol)=25 were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 10 mg of the above prepared solid component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, pressure releasing, and discharging, so that aPP resin could be obtained. See Table 6 for specific data.
Example 7
(1) Preparation of a Catalyst Component
[0220] 300 mL of TiCl 4 was placed into a reactor replaced by high-purity nitrogen, cooled to −20° C., and was added with 7 g of magnesium ethylate. The resulting mixture was stirred, and heated in stages. When the mixture was heated to 40° C., the compound DNBP (0.003 mol), and the compound 2-(3-quinolylimino)methyl-4,6-di-tert-butylphenol of the Formula II (0.003 mol) were added. The resulting mixture was kept for 2 hours, filtered, added with 100 mL of TiCl 4 , heated to 110° C., and treated for three times. After that, the mixture was added with 60 mL of hexane, and washed for three times to obtain a solid (solid catalyst component) of 6.1 g, containing 3.2% Ti, 20.8% Mg, and 49.5% Cl.
(2) Polymerization of Propylene
[0221] 2.5 mL of AlEt 3 , and 5 mL of cyclohexyl methyl dimethoxy silane enabling Al/Si (mol)=25 were placed into a stainless reactor having a volume of 5 L and replaced by propylene gas, and was then added with 10 mg of the above prepared solid component, and 1.2 NL of hydrogen gas. 2.5 L of liquid propylene was introduced into the resulting mixture. The mixture was heated to 70° C. and maintained at 70° C. for 1 hour, followed by cooling, pressure releasing, and discharging, so that a PP resin could be obtained. See Table 6 for specific data.
Example 8
[0222] The steps of the present example were the same as those of example 7 of the present group, except that the compound 2-(3-quinolylimino)methyl-4,6-di-tert-butylphenol was substituted with N-(1-naphthylmethylene)-2,6-diisopropyl aniline. See Table 6 for specific data.
Example 9
[0223] The steps of the present example were the same as those of example 1 of the present group, except that the time of the polymerization reaction was extend to 2 hours. See Table 6 for the results.
Example 10
[0224] The steps of the present example were the same as those of example 1 of the present group, except that the time of the polymerization reaction was extend to 3 hours. See Table 6 for the results.
Example 11
[0225] The steps of the present example were the same as those of example 1 of the present group, except that the amount of the added hydrogen gas was changed to 7.2 NL. See Table 6 for the results.
Example 12
[0226] The steps of the present example were the same as those of example 4 of the present group, except that the time of the polymerization reaction was extend to 2 hours. See Table 6 for the results.
Example 13
[0227] The steps of the present example were the same as those of example 4 of the present group, except that the time of the polymerization reaction was extend to 3 hours. See Table 6 for the results.
Comparative Example 1
[0228] Steps of comparative example 1 were the same as those of example 1 of the present group, except that the no 2-(2,6-dimethylphenylimino)methyl-4,6-di-tert-butylphenol was added, and that the amount of the added DNBP was 0.006 mol. See Table 6 for specific data.
Comparative Example 2
[0229] The steps of comparative example 2 were the same as those of comparative example 1 of the present group, except that the amount of the added hydrogen was changed to 7.2 NL. See Table 6 for specific data.
[0000]
TABLE 6
Catalyst Activity
Polymer
Melt Index
(Kg polymer/
Isotacticity
M.I
g catalyst)
(%)
(g/10 min)
M w /M n
Example 1
35.5
97.1
3.9
7.1
Example 2
43.2
97.6
2.4
6.8
Example 3
44.7
96.6
2.4
7.1
Example 4
43.7
97.6
2.4
7.1
Example 5
40.8
97.7
2.7
7.3
Example 6
45.6
97.2
6.0
8.1
Example 7
48.6
97.8
6.3
8.1
Example 8
47.2
98.1
6.4
8.1
Example 9
51.3
97.7
3.0
—
Example 10
73.6
98.0
3.4
—
Example 11
48.5
95.4
45.3
—
Example 12
58.8
97.3
3.1
—
Example 13
76.6
97.4
3.0
—
Comparative
32.5
98.0
1.2
3.8
Example 1
Comparative
43.8
96.3
28.6
—
Example 2
Note:
“—” in the above Table indicates that no data is available.
[0230] As can be seen from Table 6, the catalyst provided by the present invention can greatly widen the molecular weight distribution, and increase activity of the catalyst. Meanwhile, the polymer obtained has a high melt index and isotacticity. This means that the polymer obtained has a good mechanic property, flowing property, and processability. Specifically, compared with the use of only one compound B (e.g., dicarboxylic ester compound as internal electron donor in comparative example 1) as the internal electron donor, the use of the compound of Formula II of the present invention and the compound B (examples 1 to 8) as internal electron donors can widen the molecular weight distribution of the polymer, and increase catalytic activity of the catalyst. The catalyst provided by the present invention also has a good orientation ability, and the polymer has a high melt index and isotacticity. Besides, it can be seen from examples 9 to 10 and 12 to 13 that the obtained catalyst is slow in activity attenuation, and thus has a higher long-term stability. It can be seen from examples 11 and comparative example 2 that the catalyst provided by the present invention has a good hydrogen response.
[0231] From all the above examples as well as Tables 1 to 6, it can be seen that according to the present invention, the catalyst containing the imine compounds of the Formula I as electron donors is capable of widening the molecular weight distribution, enabling the obtained catalyst to have a relatively high catalytic activity and to be slow in activity attenuation, i.e., to have a higher long-term stability, and enabling the obtained polymer to have a high isotacticity and a suitable melt index. This means that the polymer obtained has a good mechanic property, flowing property, and processability. In addition, the catalyst provided by the present invention has a good hydrogen response. The catalyst is applicable to production of high-impact polymer products.
[0232] It should be noted that the examples above are provided only for illustrating the present invention, rather than restricting the present invention. The present invention is described in detail in connection with typical examples, but it should be readily understood that the expressions used herein are merely descriptive and explanatory, not prescriptive. Amendments can be made to the present invention based on the disclosure of the claims and within the scope and spirit of the present invention. While the above descriptions about the present invention involve particular methods, materials, and implementing examples, it does not means that the present invention is limited to the presently disclosed examples. On the contrary, the present invention can be extended to other methods and applications having same functions as those of the present invention.
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The present invention discloses a catalyst component for propene polymerization, comprising titanium, magnesium, halogen, and internal electron donor A, wherein said internal electron donor A is selected from the compounds as shown in Formula I,
in Formula I, R is selected from hydrogen, hydroxyl, and substituted or unsubstituted C 1 -C 30 hydrocarbyl, preferably from hydrogen, hydroxyl, and substituted or unsubstituted C 1 -C 20 alkyl, C 6 -C 30 aryl, C 6 -C 30 heteroaryl, C 7 -C 30 alkylaryl and C 7 -C 30 arylalkyl; R 1 and R 2 may be identical to or different from each other, and are selected from hydrogen and substituted or unsubstituted C 1 -C 30 hydrocarbyl, preferably from hydrogen and substituted or unsubstituted C 1 -C 20 alkyl, C 6 -C 30 aryl, C 7 -C 30 alkylaryl and C 7 -C 30 arylalkyl. According to the present invention, by using the compound as shown in Formula I as internal electron donor compound for propene polymerization, the catalyst has a higher activity, and a slow rate of delay of activity. The obtained polymer has not only a wider molecular weight distribution, but also a high melt index and isotacticity.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application refers back to provisional application Ser. No. 60/184,133 Filling date Feb. 22, 2000.
FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable
REFERENCE TO A MICROFICHE APPENDIX
[0003] Not Applicable
BACKGROUND TO THE INVENTION
[0004] 1. Field of the Invention
[0005] The invention relates to lighted hand-held instruments including: tweezers, forceps screwdrivers, pliers, wire cutters, magnifying lenses, seam rippers, ratchet assemblies and hole augers.
[0006] 2. Description of Related Art
[0007] Performing work in dim or obscure lighting often requires specialized lighting, a flashlight or lantern. This requirement compromises safety and performance when a worker must hold the lighting fixture for better viewing in limited space environments.
[0008] Many devices address these issues by attempting to provide convenient illumination means including: Neugass (U.S. Pat. No. 2,376,448), Zuckerman (U.S. Pat. No. 2,666,843), Johnson (U.S. Pat. D175,259), Spedding (U.S. Pat. No. 3,287,547) and Nalbandian (U.S. Pat. D253,974). These variations of similarly designed illuminated tweezers depict illumination means between the tweezer's prongs. The grasped area shadows when squeezing the tweezer s prongs making it difficult to view work in progress.
[0009] Cooper (U.S. Pat. No. 4,302,797) illustrates HAND TOOLS (in screwdriver form) comprising a hollowed shaft with fiber optic cables, a light bulb in the handle and a blade at the insertion point. Light passes through the blade and illuminates the area where the blade inserts into the screw head. The fiber optic lines focus light on the screw head and provide limited work area illumination.
[0010] Holoff, deceased et al. (U.S. Pat. No. 4,524,647) describes a lighted TWEEZER ASSEMBLY with a magnified viewing lens. The user wraps their palm around the device and pinches the tweezers. The magnification lens provides a functional viewing area commensurate with vertical or horizontal clearance between the user's eye(s) and the device.
[0011] Hoskin, et al. (U.S. Pat. No. 4,671,283) is a FORCEPS with a groove running along the inner face of each arm that contains fiber optic cable for tip illumination. Hoskin, et al. limits viewable area akin to Cooper wherein the cone of illumination focuses upon the actual grasping point.
[0012] Owen (U.S. Pat. No. 4,836,596) combines TWEEZERS AND MAGNIFIER wherein the parts snap together to provide efficient assembly and sterilization. The device provides no artificial illumination.
[0013] Finn, et al. (U.S. Pat. No. 5,667,473) depicts an elaborate SURGICAL INSTRUMENT AND METHOD FOR USE WITH A VIEWING SYSTEM for endoscopic surgery. This Device employs fiber optics that couple to an auxiliary viewing system. The elongated and complex device requires a monitor for visualization.
[0014] The present invention addresses these ergonomic and illumination issues with a pistol shaped grip and overhead illumination to cast unrestricted light upon a chosen work area. For example, a user may choose tweezers to pluck eyebrows or remove splinters without shadow hindrance.
[0015] The device also provides a multi-position docking feature to accommodate several types of tools ranging from forceps and screwdrivers to seam rippers and surgical instruments. This versatility translates into reduced manufacturing costs and environmental waste while improving safety and performance.
BRIEF SUMMARY OF THE INVENTION
[0016] The device comprises a pistol shaped “grip” designed to ergonomically rest in the user's palm, illumination means at a superior portion of the grip and a multi-position docking mechanism for incorporating various instruments at various user defined locations along the grip's vertical axis.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] The figures depict several, but not all, embodiments of the NON-SHADOW MULTI-POSITION LIGHTED INSTRUMENT HOLDER.
[0018] [0018]FIG. 1 is a left side view of one device embodiment.
[0019] [0019]FIG. 2A is a right side view of one device embodiment incorporating tweezers in a position in which the tweezer tip is close to the light bulb and generally aligned with the longitudinal axis of the light.
[0020] [0020]FIG. 2B is a right side view of the embodiment of FIG. 2A with the tweezers in a position in which the tweezer tip is farther from the light bulb and generally aligned with the longitudinal axis of the light.
[0021] [0021]FIG. 3 is a side view of one device embodiment incorporating a seam ripper.
DETAILED DESCRIPTION OF THE INVENTION
[0022] Referring to the Figures: Instrument holder ( 2 ) comprises grip ( 4 ), lighting ( 6 ) and multi-position invention docking system ( 8 ).
[0023] Grip's ( 4 ) ergonomic design permits comfortable placement between the thumb and fingers of a clenched fist. Its construction may utilize metals, non-metals or composite materials in whole or part. A preferred grip embodiment utilizes injection molding to form a single piece grip wherein ridges ( 10 , 10 ′, 10 ″) ergonomically fit between the user's fingers and a recess ( 12 ) accommodates the extension of palm body mass between the thumb and wrist. The grip preferably has an elongated member with broad side surfaces ( 23 and 23 ′) and relatively narrow front ( 27 ) and rear surfaces ( 29 ), with smoothed or rounded corners. Front surface ( 27 ) may curve concavely for fingers and thumb to meet and grasp the grip (middle, ring and little finger) while thumb and index finger grasp and work the tool. Rear surface ( 29 ) may curve convexly to comfortably fit against the palm regardless of the hand grasp upon the grip or the tool angle relative to the grip. Foreseeable embodiments of this design include left-handed, right-handed and ambidextrous models. Other embodiments may include an outer layer of moldable gel material for added user comfort, or more rounded/narrower grips from front to rear surfaces for accurate hand sizing.
[0024] Lighting ( 6 ) comprises an energy source, housing ( 14 ) and light emitting source ( 16 ). Lead-acid or alkaline batteries provide an ample energy source. A preferable energy source is rechargeable batteries. In this embodiment, a photo voltaic array (PVA) may attach at various grip locations for self contained charging or to a unit for linked recharging. A recharger would draw from various power supplies including 12, 24, 48 or 220 volt direct current or 120 volt alternating current whether a PVA embodiment exists.
[0025] The device housing places the light source ( 16 ) superior, and at an acute angle, to the axis of the instrument secured, whether using an integral, external or user supplied light source. Typically, for example, the tool lies at about 20-35 degrees relative to the longitudinal axis of the light and light source, to place the tool tip farther out in front of the light for a larger diameter lighted area, or at about 35-50 degrees to place the tool tip closer to the light source for a smaller diameter light area.
[0026] The light source ( 16 ) is positioned forward of the grip front surface ( 27 ) and directly above the working tip of the tool, or, more preferably, directly behind the tip ( 31 , 33 ), as shown by the tweezer ( 35 ) and seam ripper ( 37 ) placement in FIGS. 2A, 2B, and 3 . Light, therefore, radiates substantially unobstructed by the tool and by the grip and at an effective intensity around the tip ( 31 , 33 ), so that the area of skin, cloth, leather, wood, etc. being worked on and the tip ( 31 , 33 ) are well illuminated. The tool preferably may be adjusted at the docking system to adjust the location of the tool tip relative to the light radiating from the light source. In most instances, the tool is placed in the docking system so that the tool tip is generally in line with the light source, that is, aligned with the longitudinal axis of the radiating light. Then, to adjust the effective area of illumination, the tool tip is preferably moved forward or backward relative to the light, so that the area of light around the tool tip is larger (less “focused”) or smaller (more “focused” or more intense), respectively. Thus, when a sliver is being removed, one may place the tweezer tip close to the light for very intense light, or, when a seam is being ripped, one may place the seam ripper farther in front of the light for a softer, larger area of light. For example, with conventional tweezers, when the docked end ( 38 ) of the tweezer is slid or otherwise moved down in the docking system and the tweezer is slanted inward toward the grip, or at about 35-50 degrees to the longitudinal axis of the light, the tool tip is closer to the light source for an intense, smaller diameter lighted area. When the docked end 38 is slid or otherwise moved up in the docking system, and the tweezer is slanted further outward, the tool may rest roughly at 15-25 degrees relative to the longitudinal axis of the light and light source, which places the tool tip farther forward from the light for a larger diameter lighted working area. Such an adjustment of a tool in the docking system is illustrated in FIGS. 2A and 2B, wherein the tool tip is near the light bulb in FIG. 2A and farther out in FIG. 2B.
[0027] Housing for the illumination circuit may exist in several forms: A preferred method utilizes a flashlight configuration capable of holding two 1.5 volt batteries, or similar low voltage power sources, with a switch at a rearward location relative to the light source. Other embodiments include means to clamp the user's already purchased flashlight in a retrofit application. In these, and equivalent, embodiments the housing could be located internal or external to grip.
[0028] A preferred light bulb ( 18 ) is the Ray-Q-Vac (TM) RF22 for its even illumination band. Other light bulbs, fiber optic emitters, light emitting diodes (LEDs) or lasers are easily substituted. One preferred light source uses the RF22 in a red or blue-green spectrum to avoid the “night vision” loss associated with white light in dark environs.
[0029] Instrument docking system ( 8 ) may comprise many distinct embodiments including: one or more recesses with, or without, threading for a set screw ( 24 ), one or more bores at a location near the palm wherein instruments pass through the grip for affixation, a sliding clamp affixed to the grip distal to the user's palm to grasp desired implement(s), a slot ( 30 ) from the distal portion of the grip to a superior location below the light source, or a ball and socket apparatus that slides along the grip permitting snap in attachment or removal. The preferred docking system, as well as the grip, are narrow enough from side to side and from front surface to back surface so that the thumb and fingers curve comfortably and easily around them for manipulation of the tool.
[0030] A simple example of the device could easily be whittled from wood according to the grip shapes shown in FIGS. 1 - 3 . This grip has a slot ( 30 ) along the medial portion of the vertical axis extending from the base ( 41 ) of the device upwards to a medial location ( 43 ) that accepts hand-held instruments and holds them in place using frictional forces or, optionally, with an additional fastener, such as screw ( 24 ). Along the upper portion ( 45 ) of the grip a groove ( 39 ) or a bore ( 49 ) can be carved to rest a penlight or flashlight that secures to the grip using tape, hook-and-loop material, other fasteners, or friction. Thus, the preferred device holds the illumination means generally perpendicular to the length, that is, the vertical axis, of the grip. The light location relative to the grip may be fixed during manufacture and the instrument in the docking system made adjustable, as described above, to allow linear movement of the tool tip relative to the grip and the light. Alternative embodiments are envisioned wherein the light adjusts forward/backward and/or up and down relative to the grip. In any case, the light source preferably is within about 0.5-2.5 inches of the tool tip, generally directly behind the tip. The user completes the circuit for the illumination means and proceeds to utilize its instrument of choice with the benefit of an unobstructed self-supported light source. More refined examples may use injection molding, stamping or cast construction with a preference for non-conducting materials to eliminate the potential for electric shock.
[0031] Discussion of this invention referenced particular means, materials and embodiments elaborating limited application of the claimed invention. The invention is not limited to these particulars and applies to all equivalents.
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The device comprises a pistol shaped “grip” designed to ergonomically rest in the user's Palm. Illumination means at a superior portion of the grip and a multi-position docking mechanism for incorporating various instruments at various user defined locations along the grip's vertical axis. The assembly is configured to allow the user, with one hand, to illuminate the work area and use an instrument without substantially obstructing the light source.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an active matrix liquid crystal display device and, more particularly, to an active matrix liquid crystal display device in which the residual image phenomenon is prevented.
[0003] 2. Description of the Prior Art
[0004] A liquid crystal display device is adopted in many fields such as a viewfinder for a video camera, a pocket TV, a high-resolution projection TV, a personal computer, and the like. In particular, an active matrix liquid crystal display device using a thin-film-transistor (TFT) as a switching element has a major feature that it can maintain a high contrast even when it performs high-capacity display, and accordingly it has been developed and commercialized actively.
[0005] The above active matrix liquid crystal display device widely employs the TN (Twisted-Nematic)-method NW (Normally-white) mode as the liquid crystal display mode. According to the TN method, a panel, which is formed of electrode substrates sandwiching a liquid crystal layer such that liquid crystal molecules are twisted by about 90 degrees, is sandwiched between two polarizing plates. According to the NW mode, two polarizing plates are arranged such that their polarizing axes are orthogonal and become parallel or perpendicular to the major axis of liquid crystal molecules in contact with one substrate.
[0006] In this case, when no voltage is applied or a voltage equal to a threshold or less is applied, the liquid crystal display device displays white. When a voltage higher than the threshold is applied, the light transmittance of the liquid crystal display device gradually decreases, and the liquid crystal display device displays black. These display characteristics are obtained because when a voltage is applied to the liquid crystal panel, the liquid crystal molecules are modulated to be aligned in the direction of electric field while untwisting their twist structure.
[0007] Even when the molecule orientation is the same, the state of polarization of the transmitted light changes depending on the direction of incidence of light on the liquid crystal panel, so the light transmittance differs in accordance with the direction of incidence. In other words, the liquid crystal panel has view angle dependency. The view angle dependent characteristics of the TN method pose a serious problem, particularly in the image characteristics, in a large-screen liquid crystal display which has been developed widely recent years.
[0008] As a means for solving this problem, Japanese Examined Patent Publication No. 63-21907, Japanese Unexamined Patent Publication No. 7-36058, and the like propose so-called transverse electric field method IPS (In-Plane-Switching), with which an electric field is not applied in a direction perpendicular to the substrates, as in the TN liquid crystal display method, but the electric field to be applied to the liquid crystal is set substantially parallel to the substrates, and the direction of liquid crystal molecules is controlled within the substrate surfaces, thus modulating light.
[0009] With the IPS-mode liquid crystal display device, even when the user shifts his or her viewpoint, he basically sees only the directions of minor axes of the liquid crystal molecules. Hence, this liquid crystal display device is free from the view angle dependency of the “standing direction” of the liquid crystal, and a wider view angle than in a TN-mode liquid crystal display device and the like can be achieved.
[0010] A normally-black IPS liquid crystal display device (shown in FIG. 1 ) utilizing the TFT characteristics will be described as an example. Normally-black is a display method for a liquid crystal display device, with which the polarizing axes of the polarizing layers are arranged such that the display device displays black when no voltage difference is produced between a pixel electrode 24 for driving the liquid crystal and a common electrode 14 and the liquid crystal is orientated at the initial alignment angle, and such that the display device displays white when a voltage difference is applied between the pixel electrode 24 and common electrode 14 and the liquid crystal is rotated (ideally through 45 degrees) from initial alignment.
[0011] The liquid crystal is initially aligned with an inclination of about 15 degrees, as indicated by an alternate long and short dashed line, with respect to the pixel electrode 24 and common electrode 14 which form comb electrodes fitted with each other, and rotates in only a specific direction upon application of a voltage between the pixel electrode 24 and common electrode 14 . The absorbing axes of the polarizing plates are aligned with the initial alignment direction of the liquid crystal, and an appropriate retardation And (product of a refractive index anisotropy An of the liquid crystal and the effective thickness d 0 of the liquid crystal layer) is set, so the display device can perform colorless white display and black display.
[0012] Display nonuniformity called residual image often occurs in an active matrix liquid crystal display device, in which when the display device displays characters or figures, even after they are deleted, their images stay to remain on the screen for some time. In particular, in the IPS mode, residual image tends to occur very often when compared to a display method in which the direction of the electric field to be applied to the liquid crystal is set substantially perpendicular to the substrate interfaces.
[0013] As a method of solving this residual image issue, for example, according to Japanese Unexamined Patent Publication No. 7-159786, if certain conditions for the physical properties of the liquid crystal, alignment film, and insulating film are met, a time required until a display part and non-display part can be discerned after displaying the same pattern for 30 min and erasing the displayed pattern can be set to 5 min or less.
[0014] However, according to the invention described in Japanese Unexamined Patent Publication No. 7-159786, when the resistivity of the liquid crystal is sufficiently decreased, although the residual image phenomenon is decreased, if a fixed pattern is displayed for a long period of time, a residual image sometimes occurs.
[0015] Conventionally, various factors were attributed to the residual image which occurs in the IPS mode. For example, due to the necessary arrangement, electrode interconnections are formed on only the active substrate unit, and not on the opposite color filter unit. Therefore, an electric field may enter a light-shielding layer for shielding the color layer in the color filter, the electrode interconnections on the active substrate, and TFT elements, thus causing a residual image.
[0016] The operation of the TFT will be described. A TFT element serves as a switch which is turned on/off by the voltage applied to the gate electrode. When a sufficiently negative potential (approximately about −10 V although it may differ depending on the arrangement of the TFT element) is applied to the gate electrode, movement of the charges in a-Si decreases, so a signal voltage from the drain electrode is not transmitted to the source electrode. Thus, the signal voltage is not applied to a pixel electrode electrically connected to the source electrode, either.
[0017] When a sufficiently positive potential (approximately about +20 V although it may differ depending on the arrangement of the TFT element) is applied to the gate electrode, movement of the charges in a-Si increases, so a signal voltage from the drain electrode is transmitted through the source electrode and applied to the pixel electrode. When a monochromatic fixed pattern is displayed on the IPS liquid crystal display device, the potential difference between the drain and source electrodes of a TFT element in a pixel that displays white differs from the potential difference between the drain and source electrodes of a TFT element in a pixel that displays black.
[0018] Why residual image occurs will be described in more detail. For example, if the TFT element has the characteristics as shown in FIG. 2 , a residual image that a part that has displayed white becomes brighter is observed. The ON current of the TFT that has displayed white is almost equal to that of a part that has displayed black. Since only the OFF current decreases, the voltage written in the liquid crystal is discharged by an OFF current lower than that at the part that has displayed white. Therefore, the part that has displayed white becomes undesirably brighter than the part that has displayed black, because the effectively large applied voltage remains in the liquid crystal.
[0019] A phenomenon opposite to this also happens. When the ON current for the part that has displayed white decreases as shown in FIG. 3 , a phenomenon that the part that has displayed white is displayed darker occurs.
[0020] In the conventional IPS liquid crystal display device, a light-shielding layer is formed on a color filter unit side. Light entering a region (non-open portion) other than the pixel electrodes and common electrode which form comb teeth is shielded by the light-shielding layer. In the non-open region, the state of alignment of the liquid crystal is the same as that of the open region, so display is not adversely affected.
[0021] For this reason, when white is displayed, the liquid crystal on the TFT element of this pixel is rotated from the initial alignment angle. On the other hand, a liquid crystal on the TFT element of a pixel that has displayed black is not much rotated since the electric field between the drain electrode and source electrode is small.
[0022] When fixed monochromatic pattern is continuously displayed for a long period of time, the state of the liquid crystal on the TFT element changes, and is fixed. It takes a certain period of time until the changed TFT characteristics are restored. Therefore, the liquid crystal alignment on the TFT element of the pixel that has displayed black differs from that on the TFT element of the pixel that has displayed white, and the electric field enters amorphous silicon differently. This causes a difference in the TFT characteristics. Then, for example, when half-tone solid display is performed, a pattern which is the same as the previously displayed pattern is visually recognized, that is, the so-called residual image phenomenon occurs.
[0023] The present inventors found that residual image which was not conventionally solved in the liquid crystal display device was related to a change in TFT characteristics of each pixel. More specifically, according to the findings of the present inventors, when the liquid crystal display device displays a fixed pattern, a change occurs in the characteristics of the TFT element of a pixel which displays white and of the TFT element of a pixel which displays black, thus causing a residual image.
[0024] The alignment state of the liquid crystal molecules on the TFT element gradually shifts from the initial state due to the electric field generated between the drain electrode and source electrode. Due to this shift, the electric field enters the amorphous silicon portion of the TFT element differently in the case of white display and in the case of black display. As a result, the subsequent display state changes.
SUMMARY OF THE INVENTION
[0025] The present invention has been made in view of the above situation of the prior art, and has as its object to provide an active matrix liquid crystal display device in which even if the TFT element operates, the orientation of the liquid crystal on the TFT element does not change from the initial alignment angle. Therefore, a liquid crystal display device is provided in which the characteristics of the TFT element do not change during display, and even after a fixed pattern is kept displayed for a long period of time, no residual image phenomenon occurs.
[0026] Arrangements with which the liquid crystal alignment on the TFT element portion is not changed by the electric field generated between the drain electrode and source electrode will be practically described.
[0027] (1) The shapes of the drain electrode and source electrode are determined such that the direction of the electric field generated between the drain electrode and source electrode coincides with the rubbing direction. For example, the drain electrode and source electrode are formed such that their opposing edges are perpendicular to the rubbing direction. Also, the shape of amorphous silicon may be inclined to match the rubbing direction.
[0028] (2) The rubbing direction in the display region and the liquid crystal alignment on the TFT element are differed from each other, and the direction of the electric field generated between the drain electrode and source electrode and the rubbing direction are set to coincide with each other. This is achieved by, e.g., performing mask rubbing on the TFT element portion (the first and third embodiments to be described later).
[0029] (3) Rubbing is performed parallel to the longitudinal direction of the comb teeth, so the liquid crystal alignment on the TFT element coincides with the direction of the electric field between the drain electrode and source electrode (the second embodiment to be described later).
[0030] (4) The liquid crystal is rubbed by using an alignment film which can be imparted with an alignment function upon being irradiated with light (the fifth embodiment to be described later).
[0031] (5) Partial rubbing is performed by using an alignment film which can be imparted with an alignment function upon being irradiated with light (the sixth embodiment to be described later).
[0032] (6) A liquid crystal with a negative dielectric constant anisotropy is used. In this case, the liquid crystal must be imparted with initial alignment in a direction perpendicular to the direction of the electric field generated between the drain electrode and source electrode (the seventh embodiment to be described later).
[0033] (7) The drain electrode, the source electrode, and amorphous silicon are formed inclined to be parallel to the rubbing direction. (the eighth embodiment to be described later).
[0034] (8) The electric field generated by the source electrode and drain electrode in the TFT element is set parallel to the rubbing direction, and a pixel electrode and common electrode within at least the display region are formed parallel to the rubbing direction (the ninth embodiment to be described later).
[0035] (9) The electric field generated by the source electrode and drain electrode in the TFT element is set parallel to the rubbing direction, and a pixel electrode and common electrode at least within the display region are formed to have an L shape (the 10th and 11th embodiments to be described later).
[0036] In the liquid crystal display devices with the above arrangements according to the present invention, the liquid crystal alignment on the TFT element is always constant and does not change in accordance with the state of liquid crystal display. Thus, occurrence of the residual image phenomenon accompanying a change in TFT characteristics can be suppressed, so a high-quality active matrix liquid crystal display device can be provided.
[0037] The above and many other objects, features and advantages of the present invention will become manifest to those skilled in the art upon making reference to the following detailed description and accompanying drawings in which preferred embodiments incorporating the principle of the present invention are shown by way of illustrative examples.
BRIEF DESCRIPTION OF THE DRAWINGS
[0038] FIG. 1 is a plan view showing an active element substrate unit in a conventional active matrix liquid crystal display device;
[0039] FIG. 2 is a graph of TFT characteristics that change such that the OFF voltage increases;
[0040] FIG. 3 is a graph of TFT characteristics that change such that the ON voltage increases;
[0041] FIG. 4 is a plan view showing an active element substrate unit in an active matrix liquid crystal display device according to the first embodiment of the present invention;
[0042] FIG. 5 is a sectional view taken along the line V-V of FIG. 4 ;
[0043] FIG. 6 is a plan view showing an active element substrate unit in an active matrix liquid crystal display device according to the second embodiment of the present invention;
[0044] FIG. 7 is a plan view showing an active element substrate unit in an active matrix liquid crystal display device according to the third embodiment of the present invention;
[0045] FIG. 8 is a plan view showing an active element substrate unit in an active matrix liquid crystal display device according to the fourth embodiment of the present invention;
[0046] FIG. 9 is a plan view showing an active element substrate unit in an active matrix liquid crystal display device according to the seventh embodiment of the present invention;
[0047] FIG. 10 is a plan view showing an active element substrate unit in an active matrix liquid crystal display device according to the eighth embodiment of the present invention;
[0048] FIG. 11 is a plan view showing an active element substrate unit in an active matrix liquid crystal display device according to the ninth embodiment of the present invention;
[0049] FIG. 12 is a plan view showing an active element substrate unit in an active matrix liquid crystal display device according to the 10 th embodiment of the present invention;
[0050] FIG. 13 is a plan view showing an active element substrate unit in an active matrix liquid crystal display device according to the 11 th embodiment of the present invention; and
[0051] FIG. 14 is a plan view showing a modification to the eighth embodiment shown in FIG. 10 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0052] Several preferred embodiments of the present invention will be described with reference to the accompanying drawings.
[0053] FIGS. 4 and 5 show the first embodiment of the present invention. FIG. 4 is a plan view, and FIG. 5 is a sectional view taken along the line V-V of FIG. 4 .
[0054] Note that materials and numerals in the first embodiment are merely examples, and that the present invention is not limited by the following description.
[0055] As shown in FIG. 5 , a liquid crystal panel 2 is comprised of an active element substrate unit 4 , color filter unit 6 , and liquid crystal.
[0056] The active element substrate unit 4 will be described first.
[0057] Cr is sputtered to about 1,000 Å (10,000 nm) at a predetermined region on a first glass substrate (TFT substrate) 10 , and is patterned to form a scanning signal line 12 and common electrode 14 . Then, a silicon nitride film and silicon oxide film as insulators are formed on the glass substrate 10 by CVD to a total of about 5,000 Å so as to cover the scanning signal line 12 and common electrode 14 , thus forming a gate insulating film 16 .
[0058] An a-Si layer and n + a-Si layer are formed by CVD in a predetermined region to about 3,000 Å and 500 Å, respectively, and are patterned to form island-like amorphous silicon 18 .
[0059] Cr is sputtered to about 1,000 Å on the gate insulating film 16 and island-like amorphous silicon 18 , and is patterned to form a drain electrode 20 , data line 21 , source electrode 22 , and pixel electrode 24 . Thus, the island-like amorphous silicon 18 , drain electrode 20 , and source electrode 22 make up a TFT element.
[0060] As shown in FIG. 4 , the drain electrode 20 and source electrode 22 are formed such that their opposing edges are inclined by an angle θ, and an initial alignment angle Φ formed by rubbing (to be described below) and the angle θ coincide with each other. The initial alignment angle Φand angle θ are angles measured with reference to the longitudinal directions of the pixel electrode 24 and common electrode 14 (also called a comb electrode).
[0061] SiN as an insulator is formed on the entire region on the gate insulating film 16 to about 3,000 Å by CVD to form a passivation film 32 . The passivation film 32 and gate insulating film 16 are etched in a predetermined region to form a hole communicating with the scanning signal line 12 . This hole is filled with Cr or the like to form a contact (not shown). The unit formed in this manner is called the active element substrate unit 4 . Note that the widths of the pixel electrode 24 and common electrode 14 are set to 4.5 μm and that the distance between the pixel electrode 24 and common electrode 14 is set to 10 μm.
[0062] The color filter unit 6 is formed by forming a light-shielding layer 42 , color layer 44 , and planarized film 46 into a predetermined pattern in a predetermined region on the inner surface of a second glass substrate (counter substrate) 40 . A transparent conductive film 48 made of ITO or the like is formed on the lower surface of the second glass substrate 40 by sputtering in order to prevent display nonuniformity which is caused by charge-up when the operator touches the liquid crystal panel with his hand.
[0063] An alignment film 60 is formed on the surface of each of the active element substrate unit 4 and color filter unit 6 by offset printing or the like, and is subjected to rubbing by the rubbing method such that the initial alignment angle becomes Φ. In the drawings, the initial alignment direction is indicated by an alternate long and short dashed line.
[0064] An inner-cell spacer or the like (not shown) is placed between the active element substrate unit 4 and color filter unit 6 to form a predetermined gap, and a nematic liquid crystal 50 is sealed in it with a sealing agent (not shown) and a hole closing material (not shown), thus forming the liquid crystal panel 2 . Hence, the liquid crystal molecules of the nematic liquid crystal 50 are initially aligned parallel such that they are inclined with respect to the pixel electrode 24 and common electrode 14 at the angle Φ (15 degrees; the angle need not be 15 degrees but may take other values).
[0065] As the liquid crystal material, a nematic liquid crystal with a positive dielectric constant anisotropy Δε of 8.0 (589 nm, 20 degrees of Celsius thermometer), a refractive index anisotropy )n of 0.075, and a liquid crystal resistivity of 1.0×10 12 Ω cm is used. The thickness of the liquid crystal layer (cell gap) is set to 4.0 μm.
[0066] Polarizing plates 62 are arranged on the upper and lower surfaces of the liquid crystal panel 2 . Thus, the state of alignment of the nematic liquid crystal 50 is changed upon application of an external signal voltage, to control the strength of light transmitted through the liquid crystal panel 2 , so that the liquid crystal display device (not shown) performs gradation display.
[0067] When no potential difference is applied between the pixel electrode 24 and common electrode 14 , the liquid crystal display device displays black. When a potential difference is applied between the pixel electrode 24 and common electrode 14 to form an electric field almost parallel to the glass substrate 10 , and the liquid crystal is rotated through almost 45 degrees from the initial alignment angle so the strength of the transmitted light becomes the maximum, the liquid crystal display device displays white (normally-black method).
[0068] The liquid crystal panel 2 obtained in this manner was built as a liquid crystal display device in a driving unit (not shown), and was subjected to a residual image test. As shown in FIG. 4 , the drain electrode 20 and source electrode 22 of the liquid crystal panel 2 are formed such that their opposing edges are inclined at the angle θ, and the initial alignment angle Φ and the angle θ coincide with each other. Even when an electric field is generated between the drain electrode 20 and source electrode 22 , the liquid crystal molecules do not rotate. Therefore, the dielectric constant and the like between the drain electrode 20 and source electrode 22 did not differ between white display and black display, and no residual image occurred at all. Also, Φ=θ need not always be satisfied. In this case, the closer the values of Φ and θ, the more residual image can be prevented.
[0069] The second embodiment will be described with reference to FIG. 6 .
[0070] In this embodiment, an active element substrate unit 4 is formed in the following manner. A description on the same steps, members, and the like as those in the first embodiment will be omitted.
[0071] In the active element substrate unit 4 , as shown in FIG. 6 , the opposing edges of a drain electrode 20 and source electrode 22 form the right angles with the longitudinal direction of the comb electrode formed of a pixel electrode 24 and common electrode 14 , and an alignment film 60 is rubbed to have an initial alignment angle Φ. The drain electrode 20 and source electrode 22 are subjected to rubbing such that they are parallel to the longitudinal direction of the comb electrode.
[0072] Regarding this, liquid crystal molecules are aligned parallel by rubbing such that they are inclined at Φ (15 degrees) with respect to the longitudinal direction of the comb electrode. After that, a negative photosensitive resist is printed by a spin coater, and those portions of the resist which are on the drain electrode 20 and source electrode 22 are removed by photolithography. In this state, rubbing is performed, and the liquid crystal panel 2 is formed such that the liquid crystal molecules on the drain electrode 20 and source electrode 22 are aligned parallel (θ=0) to the longitudinal direction of the comb electrode.
[0073] A display device formed of the liquid crystal panel 2 obtained in this manner was subjected to a residual image test. On the drain electrode 20 and source electrode 22 , the direction of the electric field and the liquid crystal alignment coincide, in the same manner as in the first embodiment. The liquid crystal molecules are not accordingly rotated by the electric field. An apparent residual image suppression effect was confirmed.
[0074] The third embodiment will be described with reference to FIG. 7 .
[0075] In this embodiment, regarding the opposing edges of a drain electrode 20 and source electrode 22 , as shown in FIG. 7 , an initial alignment angle Φ obtained by rubbing and an inclination angle θ of the drain electrode and source electrode are set to coincide with each other, in the same manner as in the first embodiment, and island-like amorphous silicon 18 is also inclined to match the inclination angle θ. Except for these respects, the third embodiment is identical with the first embodiment. Residual image can be prevented more effectively also in this manner.
[0076] The fourth embodiment will be described with reference to FIG. 8 .
[0077] In this embodiment, as shown in FIG. 8 , the opposing edges of a drain electrode 20 and source electrode 22 are set perpendicular to the longitudinal direction of the comb electrode, and the alignment direction of entire rubbing is set parallel to the longitudinal direction of the comb electrode. Then, no rotation force is applied to the liquid crystal molecules on the drain electrode 20 and source electrode 22 by the electric field generated between the drain electrode 20 and source electrode 22 , so residual image does not occur. The open portion, i.e., the comb electrode, applies a predetermined rotation force to the liquid crystal, so arbitrary display is performed.
[0078] The fifth embodiment will be described.
[0079] In this embodiment, as alignment films 60 , those to which an aligning capability is imparted by irradiation with light (ultraviolet rays, a laser beam, or the like) are used. These alignment films may set entire alignment as described above, or the alignment direction may differ from portion to portion.
[0080] For example, an alignment film on a drain electrode 20 and source electrode 22 (on island-like amorphous silicon 18 ) is aligned by light, using a photomask, such that they are perpendicular to the opposing edges of the drain electrode 20 and source electrode 22 , i.e., such that it is parallel to the longitudinal direction of the comb electrode. At other portions, the alignment film is aligned by using another photomask such that they are inclined at Φ (15 degrees) with respect to the longitudinal direction of the comb electrode. A liquid crystal panel is formed in this manner.
[0081] When a display device formed of a liquid crystal panel 2 obtained in this manner is subjected to a residual image test, an apparent residual image suppression effect was confirmed.
[0082] According to the sixth embodiment, as alignment films 60 , those that can be imparted with an alignment capability upon irradiation with light are employed, in the same manner as in the fifth embodiment, and are aligned by light such that the entire alignment direction is parallel to the longitudinal direction of the comb electrode. More specifically, the alignment films 60 , respectively formed on the surfaces of an active element substrate unit 4 and color filter unit 6 by offset printing or the like, are irradiated with light in a predetermined direction, so as to align liquid crystal molecules such that they are parallel to the longitudinal direction of the comb electrode, thus forming a liquid crystal panel. Alternatively, the liquid crystal molecules may be aligned in other directions by light or the like.
[0083] When a display device formed of the liquid crystal panel obtained in this manner was subjected to a residual image test, an apparent residual image suppression effect was confirmed.
[0084] The seventh embodiment will be described with reference to FIG. 9 .
[0085] In this embodiment, a drain electrode 20 , source electrode 22 , and island-like amorphous silicon 18 are inclined as shown in FIG. 9 , so that they match an inclination angle θ, in the same manner as in the third embodiment. Alignment films 60 for an active element substrate unit 4 and color filter unit 6 are subjected to rubbing by the rubbing method such that they are inclined at an angle Φ (15 degrees) with respect to the widthwide direction of the comb electrode, as shown in FIG. 9 , and the liquid crystal molecules are aligned parallel.
[0086] A predetermined gap is formed between the active element substrate unit 4 and color filter unit 6 with an inner-cell spacer or the like (not shown), and a nematic liquid crystal 50 is sealed in it with a sealing agent (not shown) and a hole closing material (not shown), thus forming the liquid crystal panel. As the liquid crystal material, a nematic liquid crystal with a negative dielectric constant anisotropy Δε of −5.0 (589 nm, 20 degrees of Celsius thermometer), a refractive index anisotropy Δn of 0.075, and a liquid crystal resistivity of 1.5×10 12 Ω cm is used.
[0087] At the comb electrode portion, the liquid crystal is imparted with a rotation force by the electric field, so it changes display. Regarding the liquid crystal on the drain electrode 20 and source electrode 22 , even when a voltage is applied between the drain electrode 20 and source electrode 22 , as the dielectric constant anisotropy Δε is negative, the electric field in this direction cannot impart a rotation force. Thus, a residual image does not occur.
[0088] The eighth embodiment will be described with reference to FIG. 10 .
[0089] In this embodiment, a drain electrode 20 , source electrode 22 , and island-like amorphous silicon 18 are inclined as shown in FIG. 10 , so that they match an inclination angle θ. Regarding the drain electrode 20 and source electrode 22 , not only their opposing edges but also those portions of them which are connected to a data line 21 are also set to match the angle θ.
[0090] Rubbing is performed with a uniform angle of Φ (Φ=θ) entirely.
[0091] A liquid crystal panel 2 obtained in this manner was built as a liquid crystal display apparatus into a driving unit, and was subjected to a proper residual image test for a long period of time. No residual image occurred at all.
[0092] The ninth embodiment will be described with reference to FIG. 11 .
[0093] In this embodiment, the orientation of the comb electrode is inclined. More specifically, rubbing is performed parallel to a data line 21 and the like. Regarding a drain electrode 20 and source electrode 22 , their opposing edges are perpendicular to the rubbing direction.
[0094] In the above arrangement, when an angle N is set between the direction of the electric field of the comb electrode and the initial alignment direction of the liquid crystal molecules, no problem occurs when changing display. As the direction of the liquid crystal on the drain electrode 20 and source electrode 22 coincides with the direction of the electric field between the drain electrode 20 and source electrode 22 , no rotation force is imparted to the liquid crystal. Therefore, a residual image can be prevented.
[0095] A liquid crystal panel 2 obtained in this manner was built as a liquid crystal display apparatus into a driving unit, and was subjected to a proper residual image test for a long period of time. No residual image occurred at all.
[0096] The 10th embodiment will be described with reference to FIG. 12 .
[0097] In this embodiment, the comb electrode is formed to have an L shape. The rubbing direction is identical with that of the ninth embodiment, and is parallel to a data line 21 and the like.
[0098] In the above embodiment, at the comb electrode portion, the liquid crystal molecules are rotated in the respective directions by the electric field, so display is changed. As the direction of the liquid crystal on a drain electrode 20 and source electrode 22 coincides with the direction of the electric field between the drain electrode 20 and source electrode 22 , no rotation force is imparted to the liquid crystal. Therefore, a residual image can be prevented.
[0099] When the comb electrode is formed with this shape, a portion where the liquid crystal molecules are rotated clockwise by the electric field of the comb electrode and a portion where the liquid crystal molecules are rotated counterclockwise by the electric field of the comb electrode are formed. Since the liquid crystal molecules are rotated in two directions, orientations of the liquid crystal molecules at the open portion can be dispersed, so that the visual easiness of the screen can be improved. The L shape of the comb electrode is symmetric with respect to the rubbing direction. Alternatively, the orientations of the liquid crystals may be appropriately dispersed, or may be biased in any particular direction for the purpose of, e.g., improving the visual easiness of the screen.
[0100] When a liquid crystal panel 2 obtained in this manner was built as a liquid crystal display device into a driving unit, the rotational directions of the liquid crystal molecules compensated on the right and left sides of the L-shaped electrode. Thus, the visual angle was widened more than in either one of the above embodiments. When a residual image test was performed over a long period of time, no residual image occurred at all.
[0101] FIG. 13 shows the 11 th embodiment in which a comb electrode, a drain electrode 20 , and a source electrode 22 identical with those of the above ninth embodiment are rotated through 90 degrees. When the comb electrode and the like are formed in this manner, a display device in which residual image is suppressed and with a wide visual angle can be provided.
[0102] As has been described above, from the first to the 11th embodiments, the liquid crystal alignment on the TFT element is always constant. Therefore, residual image accompanying a change in TFT characteristics can be suppressed. The residual image suppression effect is particularly apparent in the third and eighth embodiments.
[0103] In the first, third, fifth, sixth, seventh, eighth, ninth, 10th, and 11th embodiments, the liquid crystal panel can be manufactured with the same process as that for a panel with the conventional structure. In the fourth embodiment, the driving voltage to be applied to the liquid crystal can be decreased.
[0104] In the fifth and sixth embodiments, since powder dust produced by rubbing can be eliminated, the yield in the panel manufacture can be improved.
[0105] In the 10th and 11th embodiments, since the comb electrode is formed into an L shape, the rotational direction of the liquid crystal differs between the right and left sides of the electrode or between the upper and lower sides of the electrode. Thus, coloration that occurs when the liquid crystal panel is seen obliquely can be prevented, and the view angle is widened.
[0106] FIG. 14 shows a modification to the eighth embodiment shown in FIG. 10 . In this modification, part of a scanning signal line 12 corresponding to inclined island-like amorphous silicon 18 is inclined to match the inclination of the island-like amorphous silicon 18 .
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In an active matrix liquid crystal display device, a drain and source of a TFT element for controlling power supply to a pixel electrode, are arranged so that an alignment direction of liquid crystal molecules over the source and drain does not change, thereby preventing formation of ghost images in the display. In one embodiment, an electric field generated between the source and drain is parallel to an initial non-zero alignment angle of the molecules.
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This invention was made with government support under contract No. F30602-95-C-0265, awarded by the Department of Defense. The government has certain rights in this invention.
BACKGROUND OF THE INVENTION
Modern communications techniques transmit information efficiently by modulating the information before transmission. Modulation results in signal segments (generally referred to as symbols) which may represent a single bit or multiple bits of information. For example, in QPSK modulation, each symbol represents two bits of information. The symbols are grouped into sets containing predetermined numbers of symbols. The sets are called frames and each frame typically contains specific header information including, for example, identification, routing, or error detection/correction coding. Furthermore, the symbols are typically frequency shifted by a carrier into an appropriate band (for example, the bandwidth allocated to an FM radio channel) before or during transmission.
At the receiver, the transmitted signal must be acquired before the information may be extracted. Acquiring a signal includes determining the carrier frequency, determining the symbol timing, and determining the frame timing so that the receiver may synchronize with the transmitted signal. Once the transmitted signal is acquired, the receiver must maintain synchronization as well. Acquiring the transmitted signal and maintaining synchronization, however, are often extremely difficult.
In determining the carrier frequency the receiver must be able to account for many types of masking and interference. For example, where the receiver or transmitter is moving relative to the other, the true carrier frequency may be masked by a Doppler shift. Other factors may also affect the carrier frequency, including inaccurate time bases at the transmitter, atmospheric conditions such as ambient temperature, and multi-path interference.
Assuming that the receiver has acquired the carrier frequency, the receiver must then synchronize with the symbol timing in the transmitted frame, a process often referred to as clock recovery. In the past, clock recovery has typically involved trial and error demodulation of the transmitted signal at the receiver in order to determine where individual symbol modulation begins and ends. For example, when a particular trial demodulation yields incorrect data, the receiver either advances or retards its approximation to the symbol timing and makes another attempt. Once the receiver has acquired the symbol timing, it next has to determine the frame timing.
Acquiring frame timing is analogous to determining where a complete message starts and stops. Knowing where the message starts allows the receiver to examine the frame header information commonly included with the frame. The frame header information, for example, is often important in determining what, if anything, the receiver should do with the frame. In general, once the symbol timing is acquired, the receiver may monitor the transmitted data until it recognizes the next start of frame.
Because a receiver typically does not acquire the carrier frequency and symbol timing immediately, numerous symbols or frames may pass by before the receiver is able to recover information. In burst communications, in which data is transmitted in short segments or bursts, the delay incurred at the receiver to acquire the carrier frequency, symbol timing, and frame timing may prevent the receiver from recovering any data at all. Similarly, data may also be lost in continuous transmission systems during receiver start up.
In both continuous and burst transmission systems, the receiver may also lose data trying to resynchronize to the transmitted data. Resynchronization is necessary, for example, when a drop out occurs during reception. Typical sources of drop out include physical obstructions in the signal path, for example trees, buildings, and tunnels, as well as atmospheric and electrical disturbances between the receiver and transmitter. In order to cope with drop outs, transmitters typically intersperse additional synchronization information during the transmission of normal data.
In the past, during synchronization and resynchronization, receivers have typically employed a frequency sweep technique in order to acquire the carrier frequency. In the frequency sweep technique, the receiver hypothesizes the correct carrier frequency and searches many frequencies over a predetermined uncertainty range. At each hypothesis, the receiver must try to acquire symbol timing and frame timing. If the hypothesis fails, the receiver must continue trying to acquire the carrier frequency. In the past, therefore, the frequency acquisition process often requires substantial time and processing power.
To help receivers acquire the carrier frequency, transmitters typically transmit long preambles or headers of modulated information before the frame. The headers required to allow receivers to acquire the carrier frequency with acceptable probability often introduce an overhead of as much as 30% compared to the actual data in a frame. Thus, a significant amount of bandwidth and processing time is used simply to allow the receiver to acquire the transmitted signal as opposed to actually communicating useful information. In fact, the processing power required to acquire and maintain synchronization with the transmitted signal may surpass that required to decode the actual data by a factor of 10 or more.
Therefore, a need remains in the industry for an improved signal acquisition method which overcomes the disadvantages discussed above and previously experienced.
BRIEF SUMMARY OF THE INVENTION
It is an object of the present invention to allow a receiver to acquire a transmitted signal.
It is a further object of the present invention to provide a receiver with an auto-correlation technique that may be used to acquire a transmitted signal.
It is another object of the present invention to reduce the time required for receiver to acquire a transmitted signal.
It is another object of the present invention to reduce the processing required for receiver to acquire a transmitted signal.
Still another object of the present invention is to reduce the cost and complexity associated with transmitters and receivers in a communications system.
It is an object of the present invention to significantly reduce the header required for a receiver to accurately acquire a transmitted signal.
It is yet another object of the present invention to allow a receiver to determine the carrier frequency and frame timing of a transmitted signal using symmetric chirp signals.
The signal acquisition technique of the present invention includes transmitting an auto-correlating header (“header”) followed by a data block of predetermined length followed by a symmetric auto-correlating (“trailer”). A series of such framed data blocks comprises a data frame. The lengths of the header and trailer are predetermined and may, for example, be implemented as symmetric chirp (swept frequency) signals.
At the receiver, a header reference segment (“header reference”) and a trailer reference segment (“trailer reference”) of the auto-correlating header and auto-correlating trailer are stored. Upon reception of the transmitted header, data block, and trailer, the receiver correlates the header reference with the header thereby providing a header correlation signal. In addition, the receiver correlates the trailer segment with the trailer to provide a trailer correlation signal. Peaks in the header correlation signal and trailer correlation signal are examined in conjunction with the known predetermined data block, header, and trailer lengths to acquire the data blocks and data frame. In particular, synchronization is determined for the individual data blocks comprising frames. In addition, the carrier frequency offset of the data blocks and data frame as well as the timing and positioning of the data frame itself are determined.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
FIG. 1 illustrates a chirp sync implementation of a header, a trailer, and reference segments used for comparison in the receiver.
FIG. 2 shows the effect on the correlation between the segments and the header and trailer caused by frequency shifts during transmission.
FIG. 3 shows how a block timing midpoint is determined based upon peaks in the header correlation signal and peaks in the trailer correlation signal.
FIG. 4 illustrates the definition of a frame sync 1-bit with the associated frequency and block data sync acquisition.
FIG. 5 shows the definition of a frame sync 0-bit with the associated frequency and block data sync acquisition.
FIG. 6 illustrates frame synch detection using a sequence of frame sync 0-bits, 1-bits, and x-bits that define a frame synch PN code.
FIG. 7 shows one implementation of a correlation and synchronization processor at the receiver.
DETAILED DESCRIPTION OF THE INVENTION
Turning now to FIG. 1, FIG. 1 shows a diagram of a forward chirp sync waveform 102 (“FCS”) and reverse chirp sync waveform 104 (“RCS”). In addition, a forward chirp waveform reference segment 106 (“FCS reference”) and a reverse chirp waveform reference segment 108 (“RCS reference”) are also shown.
The FCS 102 and RCS 104 possess symmetric auto-correlation properties as will be described in more detail below. The FCS 102 may be implemented, for example, as a chirp sync waveform which starts at a predetermined frequency and sweeps continuously forward to a second, higher frequency. The RCS 104 may then be implemented as the mirror image (symmetric) version of the FCS 102 . A header consists of either an RCS or an FCS and precedes the data block. A trailer consists of the symmetric waveform of the header and follows the data block. For example, if the header consists of an RCS, then the trailer will be an FCS. The specific example of an RCS and an FCS pair will be used from this point forward. It is noted, however, that the FCS and the RCS are only one example of many possible auto-correlating headers and symmetric auto-correlating trailers.
The range of frequencies over which the FCS and the RCS is swept depends on the ideal carrier frequency and on the potential range of frequency error in the carrier frequency as received at the receiver. For example, with an expected carrier frequency of 100 MHz and a range of frequency error of plus or minus 1 MHz, the FCS may sweep from 99 MHz to 101 MHz, and the RCS may sweep from 101 MHz to 99 MHz.
In principle, the potential range of frequency error may not have an easily definable upper or lower bound. As a result, an upper or lower frequency error range may be chosen to provide a given probability that the frequency error is not exceeded. Thus, for example, the 1 MHz frequency error in the above example may correspond to a 99% probability that the frequency of the transmitted signal at the receiver lies with the range 99-101 MHz.
A portion of the FCS is extracted to form the FCS reference 106 and a portion of the RCS is extracted to form the RCS reference 108 . Preferably, the FCS reference 106 and the RCS reference 108 are centered at the center frequency of the FCS and the RCS and extend in frequency to either side over a subset of the frequency range of the FCS and the RCS. For example, assuming an FCS and an RCS swept from 99 MHz to 101 MHz, the FCS reference 106 frequency extent may range from 99.8 MHz to 100.2 MHz. The RCS reference 108 frequency extent may then range from 100.2 MHz to 99.8 MHz.
The choice of frequency extent of the FCS reference 106 and the RCS reference 108 depends in part on the properties of the correlation procedure which will be discussed in more detail below. Generally, however, the correlation procedure may be implemented as the convolution of the FCS reference 106 and RCS reference 108 with the FCS and RCS. A discrete point by point dot product may also be used. The correlation procedure, for example, produces a correlation signal which peaks at the location that the FCS reference segment 106 matches the FCS. Thus, if the frequency extent is too narrow, the FCS reference 106 and the RCS reference 108 will correlate against the FCS and the RCS at many positions. On the other hand, if the frequency extent is too wide, then neither the FCS reference 106 nor the RCS reference 108 will correlate with the FCS or the RCS if there is any significant frequency error during transmission.
Turning now to FIG. 2, a diagram showing the effects of transmission frequency errors on the correlation signal is shown. A zero frequency error shift 202 , a positive frequency error shift 204 , and a negative frequency error shift 206 are shown in FIG. 2 . The zero frequency error shift 202 includes a zero shift FCS 208 (as received), a zero shift FCS reference segment 210 (stored in the receiver), and a zero shift correlator output 212 . The positive frequency error shift 204 includes a positive shift FCS 214 (as received), a positive shift FCS reference segment 216 (stored in the receiver), and a positive shift correlator output 218 . The negative frequency error shift 206 includes a negative shift FCS 220 (as received), a negative shift FCS reference segment 222 (stored in the receiver), and a negative shift correlator output 224 .
The reference segments 210 , 216 , and 222 are typically identical. In other words, only a single reference segment is stored and correlated against received FCS signals at the receiver. Preferably, the reference segment that is stored, as noted above (the FCS reference 106 ), represents a section of the ideal (zero frequency shift) carrier frequency with a predetermined frequency extent. Similarly, only a single reference segment (for example, the RCS reference segment 108 ) is typically stored and correlated against received RCS signals at the receiver.
Referring to the zero frequency error shift 202 in FIG. 2, the zero shift correlator output 212 indicates that the zero shift reference segment 210 most closely matches the zero shift FCS 208 at the center frequencies. As the zero shift reference segment 210 is correlated with portions of the zero shift FCS 208 to either side, the match is less exact, and the correlator output falls off. The magnitude of the peak in the correlation output 210 may be adjusted to any predetermined level, for example, by changing the frequency extent of the reference segments, or scaling the coefficients in the correlation process discussed below.
The receiver will typically not receive an FCS with zero frequency error. Is most instances, the frequency of the transmitted signals will shift in one direction or the other as they propagate toward the receiver. As an example, the positive frequency error shift 204 illustrates the reception of a positive shift FCS 214 (caused, for example, by the receiver moving away from the transmitter). As a result, the frequencies throughout the positive shift FCS 214 appear to the receiver to be reduced. The positive shift correlator output 218 therefore peaks at what ordinarily would be the higher frequencies of an FCS.
In a similar fashion, the negative frequency error shift 206 may be caused by the receiver moving toward the transmitter. As a result, the frequencies throughout the positive shift FCS 214 appear to the receiver to be increased. The positive shift correlator output 218 therefore peaks at what ordinarily would be the lower frequencies of the FCS. Because RCS signals are designed as symmetric versions of FCS signals, the correlator peak for the RCS moves in the opposite direction as the correlator peak for the FCS for frequency errors in a given direction.
Turning now to FIG. 3, a diagram of a first framed data block 302 affected by negative frequency error shift and a second framed data block 304 also affected by a negative frequency error shift is shown. The first framed data block 302 is transmitted as a first FCS 306 , a data block 308 (which may correspond to a symbol of information), and a first RCS 310 . In this example, the header is an FCS (FCS 306 ). The trailer is an RCS (RCS 310 ). A first FCS correlator peak 312 and a first RCS correlator peak 314 function as described above to indicate the presence of the negative frequency error shift.
Similarly, the second framed data block 304 is transmitted as a second RCS 316 , a data block 318 , and a second FCS 320 . In this example, the header is an RCS (RCS 316 ). The trailer is an FCS (FCS 320 ). A second RCS correlator peak 322 and a second FCS correlator peak 324 also indicate the presence of the negative frequency error shift. Note that in both the first framed data block 302 and the second framed data block 304 , the receiver may detect the center of the data block as the midpoint between the two correlator peaks. Thus, either a data block framed by an FCS header and an RCS trailer or a data block framed by an RCS header and an FCS trailer effectively communicates to the receiver where the center of the framed data block is located. It is also noted that the function of the FCS and the RCS are completely independent of the data blocks 308 and 318 . In other words, the data blocks 308 and 318 may contain any modulation or no modulation without influencing the operation of the correlator outputs.
Turning now to FIG. 4, a diagram of a frame sync 1-bit 400 and associated timing is shown. A frame sync 1-bit is defined as a FCS header 402 followed by a data block 404 followed by an RCS trailer 406 . An FCS correlator output 408 and an RCS correlator output 410 are also shown (and illustrate a negative frequency error shift affecting the frame sync 1-bit 400 ). As illustrated in FIG. 4, the FCS correlator output 408 and the RCS correlator output 410 may be used to determine a block data sync solution (T BDS ) as well as a frequency acquisition solution (Carrier Offset). T BDS represents the time at which the data block 404 begins and Carrier Offset represent the amount of frequency error in the frame sync 1-bit.
At time T FCO (referenced from time 0) the FCS correlator output 408 peaks and at time T RCO (referenced from time 0) the RCS correlator output 410 peaks. As illustrated in FIG. 4, T BDS may be determined as (T FCO +T RCO )/2−D, where D is a predetermined quantity representing the time required to transmit half of the data block 404 . The Carrier Offset is determined as L−(T RCO −T FCO )/2, where L is a predetermined quantity representing the block length (defined as the time between the center of the FCS 402 and the RCS 406 ). When there is zero frequency shift error, (T RCO −T FCO )−L=0 and the Carrier Offset is zero, as expected.
Turning now to FIG. 5, a diagram of a frame sync 0-bit 500 and associated timing is shown. A frame sync 0-bit is defined as an RCS header 502 followed by a data block 504 followed by an FCS trailer 506 . An RCS correlator output 508 and an FCS correlator output 510 are also shown (and illustrate a negative frequency error shift affecting the frame sync 1-bit 500 ). As illustrated in FIG. 4, the RCS correlator output 508 and the FCS correlator output 510 may be used to determine a block data sync solution (T BDS ) as well as a frequency acquisition solution (Carrier Offset). T BDS represents the time at which the data block 504 begins and Carrier Offset represent the amount of frequency error in the frame sync 0-bit.
At time T FCO (referenced from time 0) the RCS correlator output 508 peaks and at time T RCO (referenced from time 0) the FCS correlator output 510 peaks. As illustrated in FIG. 5, T BDS may be determined as (T FCO +T RCO )/2−D, where D is a predetermined quantity representing the time required to transmit half of the data block 504 . The Carrier Offset is determined as L−(T RCO −T FCO )/2, where L is a predetermined quantity representing the block length (defined as the time between the center of the FCS 502 and the RCS 506 ). When there is zero frequency shift error, L−(T FCO −T RCO )=0 and the Carrier Offset is zero, as expected.
An x-bit may be defined as an FCS header followed by a data block followed by an FCS trailer as well as an RCS header followed by a data block followed by an RCS trailer and may be used to indicate the presence of a signal. The presence of a signal and therefore repeated FCS or RCS signals may be detected because the correlator output shifts for an FCS header and an FCS trailer pair or RCS header and an RCS trailer pair will be in the same direction.
Turning now to FIG. 6, a technique for detecting frame synchronization using a pseudo random number (PN) code is depicted. Any other unique code could also be used. In FIG. 6, a frame sequence 600 is shown including a 0-bit 602 , a 1-bit 604 , a first X-bit 606 and a second X-bit 608 . A portion of a PN code 610 that will be used for frame sync is also shown. The first X-bit 606 is formed from an RCS header followed by an RCS trailer, and the second X-bit 608 is formed from an FCS header followed by another FCS trailer.
A PN code has a length that is 2 n −1 (for example 127 bits or 2 to the seventh power minus one) and a predetermined pattern that has the property that any n bits of the pattern define a unique position in the pattern. As a result, a receiver need only acquire n consecutive bits of the PN code in order to determine where in the sequence it has acquired the signal. Typically, a frame is constructed from multiple data blocks. A PN code can be used to form a series of 1-bits, 0-bits, and X-bits defining a frame that will allow the receiver to detect the signal and determine the carrier frequency, data block sync timing, signal presence, and frame sync.
As an example, in FIG. 6, the receiver is shown detecting a 0-bit 602 , a first X-bit 606 , a 1-bit 604 , and a second X-bit 608 . The detected bits are matched to a unique location in the PN code 610 to determine how far along in the frame the receiver is when it has acquired the signal. In principle, a greater number of bits (n, as noted above) may be used to establish a match in the PN code 610 . Knowing the predetermined frame length, the receiver may then start decoding data immediately, delay until the start of the next frame to begin decoding data, or recover from signal fading or dropout by reestablishing its position within the frame.
Turning now to FIG. 7, a diagram of one possible implementation of a correlation and signal acquisition circuit 700 is shown. The circuit 700 includes a memory 702 , and an address counter 704 connected to two sets of D-flip flops 706 and 708 . The circuit 700 also includes an FCS correlator 710 , an RCS correlator 712 , and a pair of comparators 714 and 716 . An Arithmetic Logic Unit (ALU) 718 is connected to the outputs of the D-flip flops 706 and 708 .
The FCS correlator 710 includes an N-tap delay line 720 with each tap connected to a multiplier in a multiplier array 722 . The individual multipliers form the product of their associated tap and coefficient input. Because the process is an auto-correlation, the coefficient inputs represent discrete sample points of the FCS reference segment and the RCS reference segment, for example, the FCS reference segment 106 and the RCS reference segment 108 . The outputs of the multiplier array 722 are added by the summer 724 . Because the FCS correlator 710 and the RCS correlator 712 may operate and may be constructed in a similar fashion, only the operation of the FCS correlator 710 will be discussed below.
As the receiver stores signal samples in the memory 702 , the address counter 704 cycles through the signal samples which are loaded into the N-tap delay line 720 . Each time a new sample is loaded, the oldest sample is discarded and the summer 724 produces a new FCS correlator 710 output. As discussed above, the correlator output generally peaks when the coefficients representing the stored FCS reference segment most precisely match the FCS as represented by the signal samples in the memory 702 .
When the FCS correlator 710 output exceeds a predetermined threshold (set by the threshold input connected to the comparator 714 ), the address at which the best match to the FCS reference segment occurs is latched by the set of D-flip flops 708 . Because sampling typically occurs at a regular rate, the address of the match may be converted to the time of the match by the ALU 718 . When, in addition, the RCS correlator 712 output exceeds the threshold, the address of the RCS match is provided to the ALU 718 in similar fashion. Then ALU 718 may then perform the calculations described above to acquire the signal.
As an example, the FCS correlator 710 and RCS correlator 712 may use 128 coefficients to represent the header or trailer reference. The FCS or RCS may then be designed to extend for a period of 256 sample points. The sampling rate may be chosen such that each tap in the N-tap delay line 720 represents one KHz of frequency uncertainty. The header and trailer reference then cover a total frequency uncertainty of 128 KHz.
The structure disclosed above with respect to FIG. 7 may be implemented in a variety of manners. For example, discrete logic may be used for each structure, or all of the structures may be implemented in a single digital signal processor (DSP). Because hardware is equivalent to software, any of the structure or equations discussed above may be implemented as any mixture of hardware elements and software elements.
The structure disclosed above with respect to FIG. 7 is only one of many possible implementations of a correlator suitable for use with the present invention. Other implementations are also suitable, some employing widely divergent technologies. For example, the invention described above may be practiced as part of a fiber optics communication system or a surface acoustic wave (SAW) system.
In a fiber optics communication system, the received waveform is typically coupled into a fiber optic cable. A Bragg grating may then be placed in the fiber optic cable and may function as a correlator. A suitable Bragg grating may be prepared using a holographic technique that writes a mask into the grating in the shape of a reference segment. The grating returns a maximum amount of light energy when the transmitted waveform most closely matches the reference segment written into the grating. Receiver electronics on one end of the fiber may then detect the Bragg correlator output peaks and obtain the frequency error, symbol timing, and frame timing as disclosed above with reference to FIGS. 4, 5 , and 6 .
As an alternative, a received signal may be launched onto the surface of a material suitable for propagating surface acoustic waves (SAWs). A correlator for the SAWs may then be constructed with detection fingers placed on the surface of the material. The detection fingers are generally laid out in the shape of the reference segment and may be used to provide a correlator output. Receiver electronics connected to the SAW material may then detect the correlator output peaks and obtain the frequency error, symbol timing, and frame timing as disclosed above with reference to FIGS. 4, 5 , and 6 .
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A method of acquiring a communications signal is provided. The method includes the steps of storing a forward chirp sync segment ( 106 ) of an auto-correlating forward chirp sync ( 102 ) and storing a reverse chirp sync segment ( 108 ) of a symmetric auto-correlating reverse chirp sync ( 104 ). A header comprising of either a forward chirp sync FCS ( 102 ) or a reverse chirp sync RCS ( 104 ), a predetermined number of data blocks comprising a data frame ( 308 ), and the symmetric auto-correlating trailer is received. The header, the data blocks, and the symmetric trailer are susceptible to frequency error. The method correlates the FCS segment ( 106 ) with the auto-correlating FCS ( 102 ) to provide a FCS correlation signal ( 312 ) and correlates the RCS segment ( 104 ) with the auto-correlating RCS ( 108 ) to provide a RCS correlation signal ( 314 ). The method determines the frequency error, symbol timing, and frame timing based upon the FCS correlation signal ( 312 ) and the RCS correlation signal ( 314 ).
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 10/723,600, filed Nov. 21, 2003, now U.S. Pat. No. 6,894,834, which is a continuation of International Application Serial No. PCT/EP02/09153, filed Aug. 16, 2002 and published in English on Feb. 27, 2003, which is still pending, and which claims priority from German Patent Application No. 101 39 177.3, filed Aug. 16, 2001, all of which are hereby incorporated by reference in their entirety.
TECHNICAL FIELD
The invention relates to an objective with mirrors whose central mirror apertures cause a pupil obscuration. An objective of the type considered herein includes two partial objectives, the first partial objective projecting a first field plane onto an intermediate image, and the second partial objective projecting the intermediate image onto a second field plane. Such objectives are used, for example, as projection objectives in microlithography or as inspection objectives for observing surfaces, in particular wafer surfaces.
BACKGROUND
Catoptric reduction objectives with a pupil obscuration and intermediate image for application in microlithographic projection exposure apparatus are disclosed in EP 0 267 766 A2. The exemplary embodiments shown in FIG. 2 and FIG. 3 of EP 0 267 766 A2 represent objectives with a first partial objective and a second partial objective. The two partial objectives in the case of FIGS. 2 and 3 constitute two mutually opposing quasi-Schwarzschild objectives with different magnification ratios. The quasi-Schwarzschild objectives are constructed from a convex and a concave mirror which in each case have a central mirror aperture. In the case of the objectives shown there, the aperture obscuration of 0.38 or 0.33 is relatively large by comparison with the image-side numerical aperture of 0.3. Moreover, the objectives have only a magnification ratio of 0.6 or of 0.4. The numerical aperture at the intermediate image is greater than in the image plane due to the configuration of the two mutually opposing quasi-Schwarzschild objectives.
A reflective projection objective for EUV (Extreme Ultraviolet) lithography with pupil obscuration, but without an intermediate image, is disclosed in U.S. Pat. No. 5,212,588. The projection objective includes a convex mirror with a central mirror aperture, and a concave mirror with a central mirror aperture. The rays emanating from the object plane are reflected four times at the two mirrors before they strike the image plane. The image-side numerical aperture is only between 0.08 and 0.3 in the case of an aperture obscuration of between 0.4 and 0.7. The magnification ratio in the exemplary embodiments is between −0.3 and −0.2.
A further reflective projection objective for EUV lithography with pupil obscuration, but without an intermediate image, is disclosed in U.S. Pat. No. 5,003,567. In this case, the projection objective comprises a pair of spherical mirrors which are coated with multilayers and have a common center of curvature. In this case, the first mirror is a convex mirror, while the second mirror is a concave mirror. However, these objectives of the Schwarzschild type have a large image field curvature, and U.S. Pat. No. 5,003,567 therefore proposes applying the structure-carrying mask (reticle) to a curved substrate.
Reflective projection objectives for EUV lithography with pupil obscuration and intermediate image are also disclosed in EP 1 093 021 A2. The first partial objective, arranged between the object plane and the intermediate image, has four or six mirrors which are inserted extra-axially except for the mirror arranged in the aperture plane. The first partial objective does not lead to pupil obscuration in this case. The second partial objective includes a convex mirror with an extra-axial mirror aperture, and a concave mirror with an extra-axial mirror aperture. The mirror which lies geometrically closest to the image plane is a convex mirror, and accordingly the thickness of the mirror substrate is greatest on the optical axis. This leads to a greater aperture obscuration when the free image-side working distance and the substrate thickness of the convex mirror are considered. In addition, convex mirrors generally have a lesser diameter than concave mirrors, since they have a diverging optical power. However, in the case of a lesser mirror diameter, the mirror obscuration, that is to say the ratio of the diameter of the mirror aperture to the diameter of the mirror, is more unfavorable.
A catoptric microscope objective with pupil obscuration, but without an intermediate image, is disclosed in U.S. Pat. No. 4,863,253. It includes a convex mirror without a central mirror aperture, and a concave mirror with a central mirror aperture. In this arrangement, after reflection at the concave mirror the rays do not pass through a mirror aperture in the convex mirror, but are guided past the first mirror on the outside. This leads to a very high aperture obscuration by the convex mirror.
The publication entitled “Aplanatic corrector designs for the extremely large telescope” by Gil Moretto (Applied Optics; Vol. 39, No. 16; 1 Jun. 2000; 2805–2812) discloses a mirror telescope which has, downstream of a spherical primary mirror, a correction objective which corrects the spherical aberration and coma caused by the primary mirror. In this case, the correction objective projects the intermediate image formed by the primary mirror onto the image plane of the telescope enlarged with a magnification ratio of 3.5. The objective includes two concave mirrors which project the intermediate image onto a further intermediate image, and a pair of mirrors composed of a concave mirror and a convex mirror which project the further intermediate image onto the image plane of the telescope. The projection of the intermediate image formed by the primary mirror onto the further intermediate image has a reduction ratio of −0.9, while the projection of the further intermediate image onto the image plane of the telescope is enlarged with a magnification ratio of −3.75. The numerical aperture is 0.1 at the image plane of the telescope and 0.345 at the intermediate image. Because of the mirror apertures, the objective has a pupil obscuration which is relatively large by comparison with the numerical aperture. The correction objective also has a relatively large field curvature, since the convex mirror has only a slight curvature.
A correction objective for a telescope is also disclosed in the publication entitled “Optical design of the Hobby-Eberly Telescope Four Mirror Spherical Aberration Corrector” by R. K. Jungquist (SPIE Vol. 3779, 2–16, July 1999). The optical design is very similar to the previously described correction objective. It is exclusively concave mirrors that are used in the correction objective shown, and so the field curvature is relatively large.
Controllable micromirror arrays are disclosed in the publication entitled “Digital Micromirror Array for Projection TV” by M. A. Mignard (Solid State Technology, July 1994, pp. 63–68). Their use as object to be projected in projection exposure apparatus forms the content of patents U.S. Pat. No. 5,523,193, U.S. Pat. No. 5,691,541, U.S. Pat. No. 6,060,224 and U.S. Pat. No. 5,870,176. In the exemplary embodiments described there, the respective projection objective is, however, illustrated only diagrammatically. Concrete exemplary embodiments for projection objectives which are adapted to the requirements of so-called maskless lithography are not contained in the patents.
A catadioptric projection objective with pupil obscuration and intermediate image is disclosed in DE 197 31 291 C2. In this case, the objective has a refractive and a catadioptric partial objective, and is used in a wide UV wavelength region. In addition to lenses for color correction, a concave mirror and an approximately plane mirror are arranged in the catadioptric partial objective. Because of the use of lenses, it is not possible to use this objective in the case of EUV wavelengths (<20 nm). The projection objective is used, for example, in an inspection system for observing wafer surfaces.
OBJECT OF THE INVENTION
It is an object of the invention to improve projecting objectives with pupil obscuration, in particular to reduce the aperture obscuration.
SUMMARY OF THE INVENTION
In accordance with the present invention, a projection exposure apparatus includes an illuminating system to illuminate a drivable micromirror array and an objective which projects the drivable micromirror array onto the photosensitive substrate. The objective includes mirrors which are arranged coaxial with respect to a common optical axis.
The objective can be a catoptric objective and can have a numerical aperture at the substrate greater than 0.1.
In another aspect, a projection exposure apparatus according to the present invention includes an illuminating system to illuminate a drivable micromirror array and an objective, which projects the drivable micromirror array onto a photosensitive substrate. The objective is a catoptric objective with an imaging scale ratio of greater than 20:1.
In yet another aspect, a projection exposure apparatus according to the present invention includes an illuminating system to illuminate a drivable micromirror array and an objective, which projects the drivable micromirror array onto a photosensitive substrate. The objective includes at least two partial objectives with an intermediate image plane between the at least two partial objectives.
In addition, the objective can be an objective with pupil obscuration and can consist of mirrors that are coated with reflecting layers which are adapted to reflect two mutually separated operating wavelengths.
BRIEF DESCRIPTION OF THE DRAWINGS
A more detailed description of the invention follows below, making reference to the drawings, wherein:
FIG. 1A represents a sectional view of a first exemplary embodiment of the invention;
FIG. 1B represents an enlarged detail of FIG. 1A ;
FIG. 2A represents a sectional view of a second exemplary embodiment of the invention;
FIG. 2B represents an enlarged detail of FIG. 2A ;
FIG. 3A represents a sectional view of a third exemplary embodiment of the invention;
FIG. 3B represents an enlarged detail of FIG. 3A ;
FIG. 4 schematically illustrates a lithographic projection apparatus with a controllable micromirror array;
FIG. 5 schematically illustrates a lithographic projection apparatus with a structure-carrying mask; and
FIG. 6 schematically illustrates an inspection system.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
An objective according to the invention that meets the foregoing objective includes a first partial objective and a second partial objective which are arranged along an optical axis. The first partial objective, which includes a first convex mirror with a first central mirror aperture and a second concave mirror with a second central mirror aperture, projects a first field plane onto an intermediate image. Light rays which emanate from the first field plane first pass through the second mirror aperture, are then reflected at the first mirror, next reflected at the second mirror, and then pass through the first mirror aperture. Since the diameter of the second mirror aperture is decisively determined by the diameter of the first mirror, it is advantageous for the purpose of reducing the aperture obscuration to provide the first mirror as convex mirror and the second mirror as concave mirror so that the first mirror has a substantially lesser diameter than the second mirror.
The first mirror and the second mirror are arranged at a first axial distance from each other. If not otherwise stated, in this application the axial distance between two mirrors is determined between the surface vertices of the two mirrors. In the case of mirrors with central mirror apertures, the surface vertex specifies the point on the optical axis at which the mirror surface would intersect the optical axis if the mirror had no mirror aperture. The second mirror has a second axial distance from the intermediate image. The location of the intermediate image is given by the paraxial position of the intermediate image. In order to keep the aperture obscuration as low as possible, the ratio of first axial distance to second axial distance has a value of between 0.95 and 1.05, in particular between 0.98 and 1.02. In this case, the intermediate image is located at least approximately at the location of the first mirror. Since the diameter of a ray pencil is minimal in field planes, and the pencil diameter is determined by the diameter of a mirror aperture on the other hand, it is advantageous to place the intermediate image as close as possible to the location of the first mirror. The intermediate image can therefore also be located, for example, between the first mirror and the second mirror, at the surface vertex of the first mirror or downstream of the surface vertex of the first mirror in the direction of the light, in which case the axial distances should conform to the above-mentioned condition.
The intermediate image is projected onto a second field plane by means of the second partial objective. This has the purpose of providing between the optical components of the second partial objective and the second field plane a sufficiently large free optical working distance, which does not exist between the intermediate image and the optical components of the first partial objective. The second partial objective has a third concave mirror with a third central mirror aperture and a fourth concave mirror with a fourth central mirror aperture, which are arranged facing one another. In this case, light rays first pass through the fourth mirror aperture, are reflected at the third mirror, are subsequently reflected at the fourth mirror, and then pass through the third mirror aperture. In order to keep the aperture obscuration as low as possible, the third mirror is arranged as close to the second field plane as is allowed by the free optical working distance. In addition, the third mirror is a concave mirror with a relatively large diameter, and thus the ratio of the diameter of the mirror aperture to the diameter of the mirror assumes smaller values. The axial distance between the third mirror and the second field plane is denoted below by Z M3-IM . The distance Z M3-IM advantageously has a minimum value which is equal to the sum of the minimum substrate thickness of the third mirror and a minimum free optical working distance. The minimum substrate thickness is specified on the optical axis between the surface vertex and the rear surface even if, because of the central mirror aperture, the mirror has no substrate material there. The minimum substrate thickness is 3% of the diameter of the mirror. Since it is a concave mirror, the physically present substrate thickness of the third mirror is greater. If the aperture obscuration so permits, it is advantageous when the minimum substrate thickness on the axis is 5% or even 10% of the diameter of a concave mirror with central mirror aperture. The minimum free optical working distance between the rear surface of the third mirror and the second field plane is 5.0 mm. This free optical working distance ensures the positioning of an object in the second field plane. The maximum value of the distance Z M3-IM is primarily a function of the tolerable aperture obscuration and secondly of the numerical aperture NA in the second field plane. It is advantageous for a low aperture obscuration when the diameter of the third mirror aperture is smaller than 50% of the diameter Du M3 of the third mirror. Since the diameter of the third mirror aperture increases linearly with the tangent of the arcsine of the numerical aperture in the second field plane, and with the distance of the third mirror from the field plane, the maximum value of the distance Z M3-IM is given by the following relationship:
Z
M3
-
IM
max
=
0.25
·
Du
M3
tan
(
arcsin
(
NA
)
)
.
In order to be able to use the objective for projecting an extended object onto an image in a projection exposure apparatus or in an inspection system, for example, the field curvature of the objective should be corrected as well as possible. The objective advantageously has a Petzval radius whose absolute value is greater than the axial distance between the first and second field planes. In order to compensate for the positive contributions of the concave mirrors to the Petzval sum, the first convex mirror supplies a large negative contribution. Since the first convex mirror therefore has a large negative optical power and thus, by comparison with the concave mirrors, a small diameter, this mirror is particularly critical with regard to its contribution to the aperture obscuration. However, since it is arranged at least approximately at the location of the intermediate image, the objective has a low aperture obscuration despite a good Petzval correction.
Only light rays with aperture angles starting from a specific minimum value contribute to the projection in this objective with pupil obscuration. The aperture angles are measured with reference to the optical axis. The minimum aperture angle results for the light ray which is still transmitted by all mirrors and not vignetted by a mirror aperture. The light rays are not directly vignetted by the mirror apertures, but pass as false light through the latter and strike a special light blocking device, while the remaining rays of a ray pencil with larger aperture angles are reflected by the mirrors. The aperture obscuration is defined as the ratio of the sine of the minimum aperture angle in the second field plane to the numerical aperture in the second field plane. Values of less than 0.6, in particular less than 0.5, can be achieved for the aperture obscuration by means of the arrangement of the intermediate image in the vicinity of the first mirror, and with the use of a concave mirror in the vicinity of the second field plane.
In addition to a low aperture obscuration, a large value for the ratio of the numerical aperture in the second field plane to the aperture obscuration is also an important feature of the objective. The larger the numerical aperture of the objective in the second field plane, the more difficult it is to achieve a low aperture obscuration. The objective is distinguished in that this ratio is greater than 1.2, in particular greater than 1.5.
The numerical aperture in the second field plane is greater than 0.3, in particular greater than 0.4, with particular preference greater than 0.6.
Between the first field plane and the second field plane, the objective has an imaging ratio of greater than 4:1, in particular greater than 10:1, with particular preference greater than 20:1. Imaging ratio of between 4:1 and 10:1 are typical for projection objectives for lithography. Imaging ratio of greater than 20:1 are of interest, for example, for microscope objectives, inspection objectives or projection objectives which project a controllable micromirror array onto a photosensitive substrate. In this context, the imaging ratio between two conjugated field planes is defined as the absolute value of the ratio between an object height and an image height, wherein the magnification ratio between two conjugated field planes is defined as the ratio between an image height and an object height, having e.g. a positive sign for an upright image and a negative sign for an inverted image.
Since the objective includes two partial objectives, it is advantageous when both the imaging ratio between the first field plane and the second field plane and also the imaging ratio between the intermediate image and the second field plane are greater than 1:1, in particular greater than 1.1:1. As a result, the numerical aperture between the first field plane and the second field plane is increased step-by-step. The maximum numerical aperture therefore does not occur until in the second field plane.
In order to keep the aperture obscuration as low as possible, it is advantageous if, between the first field plane and the intermediate image, the first partial objective has an imaging ratio which is substantially greater by comparison with the second partial objective. Thus, this imaging ratio should be greater than 3:1, in particular greater than 5:1, with particular preference greater than 10:1.
Due to the negative optical power of the first mirror, it is possible to make the diameter of the second mirror substantially larger than the diameter of the first mirror. The ratio of the diameter of the second mirror to the diameter of the first mirror should be greater than 3:1, in particular greater than 5:1. Since the diameter of the mirror aperture of the second mirror is approximately equal to the diameter of the first mirror, the second mirror leads only to a low aperture obscuration, or to no increase in the aperture obscuration, which is caused by the other mirrors.
Since the pencil cross section of the light rays is smallest in the region of the intermediate image, and thus also in the region of the first mirror, it is advantageous to arrange the fourth mirror in the region of the intermediate image, or in the region of the first mirror. The axial distance between the fourth mirror and the first mirror should be less than 10% of the axial distance of the first field plane from the second field plane. Unless otherwise stated, dimensions in this application are given not in absolute terms, but are stated as ratios relative to the axial distance between the first and second field planes, since all dimensions can be scaled up or down proportionally with this distance. In this case, it can be advantageous to arrange the first mirror in the mirror aperture of the fourth mirror. The two mirrors can also have the same mirror substrate, with the mirror surface of the first mirror on the front surface of the mirror substrate, and the mirror surface of the fourth mirror on the rear surface of the mirror substrate.
In an advantageous embodiment, the previously described features are achieved with only four mirrors.
In order to be able to increase the numerical aperture between the first field plane and the second field plane in two steps, a further intermediate image is advantageously arranged between the intermediate image and the second field plane. For this purpose, a fifth mirror with a fifth central mirror aperture and a sixth mirror with a sixth central mirror aperture are arranged optically between the intermediate image and the further intermediate image. The light rays first pass through the sixth mirror aperture, are reflected at the fifth mirror, are reflected at the sixth mirror, and then pass through the fifth mirror aperture. The third mirror and the fourth mirror are located optically between the further intermediate image and the second field plane. The second partial objective therefore has two subsystems, the first subsystem comprising the optical components between the intermediate image and the further intermediate image, in particular the fifth mirror and the sixth mirror, and the second subsystem comprising the optical components between the further intermediate image and the second field plane, in particular the third mirror and the fourth mirror.
When the fifth mirror and the sixth mirror are concave mirrors, they can have relatively large diameters by comparison with the mirror apertures. Thus, they worsen the aperture obscuration only slightly, if at all. As concave mirrors, they are arranged facing one another.
As an alternative possibility, the fifth mirror can be a convex mirror and the sixth mirror a concave mirror. In this case, the fifth mirror and the sixth mirror have an arrangement similar to the first mirror and the second mirror.
In order for the ray pencil coming from the sixth mirror to have a small ray diameter at the fifth mirror, and thus also for the fifth mirror aperture to have only a small diameter, it is advantageous if the distance of the further intermediate image from the fifth mirror is less than 5% of the axial distance of the first field plane from the second field plane.
Since the numerical aperture at the intermediate image is substantially greater than in the first field plane, the sixth mirror should be arranged close to the intermediate image, or close to the first mirror. The axial distance of the sixth mirror from the first mirror is advantageously less than 10% of the axial distance of the first field plane from the second field plane.
For the same reason, the fourth mirror should be arranged close to the further intermediate image, or close to the fifth mirror. The axial distance of the fourth mirror and the fifth mirror is advantageously less than 10% of the axial distance of the first field plane from the second field plane.
With the arrangement of at least six mirrors, in particular exactly six mirrors, it is possible to achieve in the second field plane a numerical aperture greater than 0.6, in particular greater than 0.8 in conjunction with an aperture obscuration of less than 0.5.
If the object to be projected is a reflective object, the illuminating light must be introduced between the first field plane and the optical components of the first partial objective. Precisely in the case of EUV wavelengths of less than 20 nm, it is advantageous to use a so-called grazing-incidence mirror to introduce the illuminating light, where the angle of incidence for the light rays is more than 70° (measured from the normal vector of the mirror surface). A sufficiently large free working distance upstream of the first field plane is, however, necessary for such mirrors. This free working distance is advantageously greater than 20% of the axial distance between the first and second field planes.
With the objective of the foregoing description, it is possible to correct the projection for a field with a diameter of greater than 1.0 mm in the second field plane.
In particular, the ratio between the spherical aberration and the axial distance between the first and second field planes is less than 10 −5 . The value of the spherical aberration represents the third-order spherical aberration according to the Seidel theory, i.e., the lateral aberration as calculated, for example, by the commercially available optical design software CodeV.
To use the objective as a projection objective or as an inspection objective, it is advantageous if the axial distance of the first field plane from the second field plane is at most 3000 mm.
If the objective has only mirrors, its application is not limited to a specific range of wavelengths. Rather, it is possible by means of an appropriate coating of the mirrors to adapt the objective to the wavelength that is being used. The objective can also be used simultaneously at two separated operating wavelengths if the reflective coatings allow this. In the case of projection objectives of a lithographic projection exposure apparatus, the projection can be performed, for example, at a first wavelength, and the alignment of structure-carrying mask (reticle) and photosensitive substrate (wafer) can be performed at a second wavelength. It is advantageous to use the objective at wavelengths of less than 200 nm, since in the case of these wavelengths only a few transparent materials such as, for example, fluoride crystals are available. The use of mirrors is mandatory in the case of wavelengths of less than 20 nm. At an operating wavelength of approximately 11 nm–13 nm, for example, mirrors with reflective multilayer coatings of molybdenum and silicon, or molybdenum and beryllium are used.
The application of the concept is not limited to purely reflective objectives. It is also possible to arrange lenses between the individual mirrors, particularly in the region of the field planes and in the region of an intermediate image. These lenses can be used, for example, to perform the color correction or to set the telecentricity.
In a preferred embodiment, the objective has a magnification ratio with an absolute value of less than 1.0. In this case, the projection of an object in the first field plane produces a reduced image in the second field plane.
Such objectives are used, for example, as projection objectives in lithographic projection exposure apparatus. In a lithographic projection exposure apparatus, an illuminating system illuminates a structure-carrying mask (reticle) which is projected by the projection objective onto a photosensitive substrate.
Such lithographic projection exposure apparatus are adequately known from the prior art, being disclosed, for example, for EUV lithography in U.S. Pat. No. 5,212,588, U.S. Pat. No. 5,003,567 or EP 1 093 021 A2, whose content is incorporated herein by reference.
Microstructured semiconductor components are fabricated in a multiplicity of individual, very complex method steps. An important method step relates to the exposure of photosensitive substrates (wafers), for example silicon substrates provided with photoresist. In this case, the reticular structure of the mask is projected onto the wafer by the projection objective during fabrication of a single so-called layer.
It is also possible to use a controllable micromirror array instead of a reticle in a lithographic projection exposure apparatus. Such lithographic projection exposure apparatus are adequately known from the prior art, being disclosed, for example, in U.S. Pat. No. 5,523,193, U.S. Pat. No. 5,691,541, U.S. Pat. No. 6,060,224 and U.S. Pat. No. 5,870,176, whose content is incorporated herein by reference. Since the previously described objectives permit an imaging ratio of greater than 20:1 between the controllable micromirror array and a photosensitive substrate, the images of the individual micromirrors, whose size is of the order 1 μm, have dimensions of less that 50 nm. Consequently, controllable micromirror arrays also are of interest for microlithography, since it is possible to implement resolutions of less than 100 nm.
In the fabrication of a single layer of a micro-structured semiconductor component, the positions of the micromirrors are controlled in accordance with a prescribed pattern in such a way that only the ray pencils of those micromirrors which are to be projected are aimed into the entrance pupil of the objective. All other ray pencils are prevented from contributing to the projection by a suitable ray trap.
It should be noted that the objective according to the invention is not restricted to one sense of direction of the light path, but can also be used in an arrangement where the light rays emanate from the second field plane and a projected image is produced in the first field plane. In a preferred embodiment of this concept, the objective has a magnification ratio whose absolute value is greater than 1.0. In this case, an object arranged in the second field plane is projected into the first field plane to produce an enlarged image.
Such objectives are used, for example, as inspection objectives in an inspection system for observing a surface of an object. The surface of the object, in particular the surface of a wafer, is projected by the inspection objective with a large magnification ratio onto the entry surface of an observation unit. The inspection system has an illuminating system which illuminates the surface directly or through the inspection objective. In the latter case, the illuminating light is, for example, introduced into the projecting beam path between the entry surface of the observation unit and the inspection objective, or inside the inspection objective. The light reflected by the wafer surface is evaluated according to various criteria by means of the observation unit.
Such inspection systems are adequately known from the prior art, being disclosed, for example, for the UV wavelength region in DE 197 31 291 C2, whose content is incorporated herein by reference.
In addition to the application as projection objective or as inspection objective, the objective according to the invention can also be used in other optical arrangements where a diffraction-limited projection is to be achieved in conjunction with very large numerical apertures, particularly in the case of EUV wavelengths. Microscopy, in particular, offers a wide field of applications.
FIG. 1A illustrates a first exemplary embodiment for an objective 1 in accordance with the invention. A detail view without the large free working space on the object side is presented in FIG. 1B for the purpose of a clearer illustration. The optical data for the first exemplary embodiment are listed in Table 1 in the format of the optical design software CodeV.
The objective 1 includes the first partial objective 3 and the second partial objective 5 , which are centered about the optical axis OA. The objective 1 projects the first field plane 7 with an imaging ratio of 100:1 onto the second field plane 9 . The numerical aperture NA in the second field plane 9 is 0.7. The diameter of the field in the second field plane 9 is 2 mm. The axial distance between the first field plane 7 and the second field plane 9 is 2000 mm.
The first partial objective 3 projects the first field plane 7 with an imaging ratio of 74:1 onto the intermediate image 11 . It includes the convex mirror 13 with the central mirror aperture 15 , and the concave mirror 17 with the central mirror aperture 19 . The concave mirror 17 is designed in such a way that the intermediate image 11 is formed in the vicinity of the convex mirror 13 . The axial distance between the mirror 17 and the paraxial position of the intermediate image 11 is equal to the axial distance between the mirror 17 and the mirror 13 and is 68.8 mm. The ratio of the diameter of the concave mirror 17 to the diameter of the convex mirror 13 is 3.0:1. The free optical working distance between the first field plane 7 and the mirror 17 is 1580 mm, assuming a substrate thickness of 35.2 mm on the optical axis for the mirror 17 .
The second partial objective 5 projects the intermediate image 11 onto the second field plane 9 with an imaging ratio of 1.35:1. It includes the concave mirror 21 with the central mirror aperture 23 , and the concave mirror 25 with the central mirror aperture 27 . The mirror 21 is arranged close to the second field plane 9 and has an axial distance of 40.0 mm from this plane. The mirror 21 has a diameter of 315.8 mm. Consequently, it should have a substrate thickness of 9.5 mm, at least on the optical axis OA. The substrate thickness of the mirror 21 on the optical axis is 30 mm. The difference between the substrate thickness and the axial distance of the mirror 21 from the second field plane 9 represents the free optical working distance, which is 10.0 mm in the first exemplary embodiment. On the other hand, the mirror 21 is arranged so close to the second field plane 9 that the mirror obscuration is only 0.3 in the case of a numerical aperture NA=0.7 in the second field plane 9 . The mirror obscuration is represented by the ratio of the diameter of the mirror aperture 23 to the diameter of the mirror 21 . So that the concave mirror 25 does not worsen the aperture obscuration, it is arranged in the vicinity of the convex mirror 13 , or of the intermediate image 11 . The axial distance between the concave mirror 25 and the convex mirror 13 is 71.3 mm.
Located between the concave mirror 21 and the concave mirror 25 is the aperture plane 29 and the light blocking device 31 , which is designed as a ray trap. The diameter of the light blocking device 31 is fixed in such a way that the ray pencils occurring in the second field plane 9 have an aperture obscuration almost independent of field height. If a mechanical shutter diaphragm with variable diameter is arranged in the aperture plane 29 , the shutter blades can move on a curved surface in accordance with the curvature of the aperture plane. It is also possible to provide a plurality of flat mechanical diaphragms with variable diameter which can be inserted if required axially offset. The marginal rays 37 and 39 , which emanate from the two field points 33 and 35 in the first field plane 7 , go through the upper and lower margins of the aperture plane 29 . The field point 33 is located on the optical axis OA, and the field point 35 is located on the upper margin of the field at a distance of 100 mm from the optical axis OA. Further illustrated for the field point 33 are the rays 41 which are just no longer vignetted by the mirror apertures. In the second field plane 9 , they have an aperture angle of 18.4°, and so the aperture obscuration is 0.45. The ratio of the numerical aperture in the second field plane to the aperture obscuration is therefore 1.56. The mirror aperture 19 of the concave mirror 17 acts in a limiting fashion for the aperture obscuration in the first exemplary embodiment.
It was possible in the first exemplary embodiment largely to correct the field curvature by means of the negative optical power of the convex mirror 13 . The Petzval radius is 192137 mm.
It was possible in the first exemplary embodiment to correct the third-order spherical aberration to a value of 0.6 μm.
A second exemplary embodiment of an objective 201 in accordance with the invention is illustrated in FIG. 2A . FIG. 2B shows a detail from FIG. 2A for the purpose of better illustration. The optical data for the second exemplary embodiment are specified in Table 2 in the format of the optical design software CodeV. The elements in FIG. 2 A/B which correspond to the elements of FIG. 1 A/B have the same reference symbols as in FIG. 1 A/B increased by the number 200. Reference is made to the description relating to FIG. 1 A/B for a description of these elements.
The objective 201 includes the first partial objective 203 and the second partial objective 205 , which are arranged centered about the optical axis OA. The objective 201 projects the first field plane 207 with an imaging ratio of 100:1 onto the second field plane 209 . The numerical aperture NA in the second field plane 209 is 0.9. The diameter of the field in the second field plane 209 is 2 mm. The axial distance between the first field plane 207 and the second field plane 209 is 2000 mm.
The first partial objective 203 projects the first field plane 207 with an imaging ratio of 52:1 onto the intermediate image 211 . It includes the convex mirror 213 with the central mirror aperture 215 , and the concave mirror 217 with the central mirror aperture 219 . The concave mirror 217 is designed in such a way that the intermediate image 211 is formed in the vicinity of the convex mirror 213 . The axial distance between the mirror 217 and the paraxial position of the intermediate image 211 is equal to the axial distance between the mirror 217 and the mirror 213 and is 447.5 mm. The ratio of the diameter of the concave mirror 217 to the diameter of the convex mirror 213 is 14.4:1. The free optical working distance between the first field plane 207 and the mirror 217 is 1050 mm, assuming a substrate thickness of 36.4 mm on the optical axis OA for the mirror 217 .
The second partial objective 205 projects the intermediate image 211 onto the second field plane 209 with an imaging ratio of 1.9:1. The projection is performed via an intermediate projection of the intermediate image 211 onto the further intermediate image 243 . The intermediate image 211 is projected by the concave mirror 245 with the central mirror aperture 247 , and by the concave mirror 249 with the central mirror aperture 251 , onto the further intermediate image 243 which is projected, in turn, by the concave mirror 221 with the central mirror aperture 223 , and by the concave mirror 225 with the central mirror aperture 227 , onto the second field plane 209 . It is possible by means of this further intermediate projection to increase the numerical aperture in the field planes step by step such that it was finally possible to achieve a numerical aperture of 0.9 in the second field plane 209 .
In order to keep the aperture obscuration as low as possible, the mirrors in the second partial objective 205 are arranged geometrically in the vicinity of field planes in each case. The optical power of the concave mirror 249 is designed in such a way that the further intermediate image 243 is formed in the vicinity of the concave mirror 245 . The axial distance between the mirror 249 and the paraxial position of the further intermediate image 243 is equal to the axial distance between the mirror 249 and the mirror 245 , and is 60.6 mm.
In order to keep the aperture obscuration as low as possible, the concave mirrors 249 and 225 are arranged in the vicinity of the intermediate image 211 , or of the further intermediate image 243 . The axial distance between the concave mirror 249 and the intermediate image 211 is 50.0 mm, and likewise 50.0 mm between the concave mirror 225 and the further intermediate image 243 . These axial distances also correspond in each case to the axial distances in relation to the mirror 213 , or to the mirror 245 . The axial distances are selected to be large enough to accommodate the adjacent mirrors 213 and 249 , or 245 and 225 , with an axial distance of the mirror rear surfaces, taking account of the respective substrate thickness. The substrate of mirror 245 does not have a plane rear surface. In order for the rays passing through the mirror aperture 247 not to be vignetted at the substrate, the rear surface has a frustoconical depression surrounding the central mirror aperture 247 .
The mirror 221 is arranged close to the second field plane 209 and has an axial distance of 40.0 mm from this plane. The mirror 221 has a diameter of 748.2 mm. Consequently, it should have a substrate thickness of 22.4 mm, at least on the optical axis OA. The substrate thickness of the mirror 221 on the optical axis is 34 mm. The difference between the substrate thickness and the axial distance of the mirror 221 from the second field plane 209 represents the free optical working distance, which is 6.0 mm in the second exemplary embodiment. On the other hand, the mirror 221 is arranged close enough to the second field plane 209 that the mirror obscuration is only 0.27 with a numerical aperture NA=0.9 in the second field plane 209 .
The aperture plane 229 with the light blocking device 231 is located between the concave mirror 221 and the concave mirror 225 . The marginal rays 237 and 239 , which emanate from the two field points 233 and 235 in the first field plane 207 , go through the upper and lower margins of the aperture plane 229 . The field point 233 is located on the optical axis OA, and the field point 235 is located on the upper margin of the field at a distance of 100 mm from the optical axis OA. The aperture obscuration is 0.43 in the second exemplary embodiment. The ratio of the numerical aperture in the second field plane to the aperture obscuration is therefore 2.09. The mirror aperture 251 of the concave mirror 249 is the limiting factor for the aperture obscuration in the second exemplary embodiment.
It was possible in the second exemplary embodiment largely to correct the field curvature by means of the negative optical power of the convex mirror 213 . The Petzval radius is 8940 mm.
It was possible in the second exemplary embodiment to correct the third-order spherical aberration to a value of 0.8 μm.
A third exemplary embodiment of an objective 301 in accordance with the invention is illustrated in FIG. 3A . FIG. 3B shows a detail from FIG. 3A for the purpose of better illustration. The optical data for the third exemplary embodiment are specified in Table 3 in the format of the optical design software CodeV. The elements in FIG. 3 A/B which correspond to the elements of FIG. 2 A/B have the same reference symbols as in FIG. 2 A/B increased by the number 100. Reference is made to the description relating to FIG. 2 A/B for a description of these elements.
The objective 301 includes the first partial objective 303 and the second partial objective 305 , which are centered on the optical axis OA. The objective 301 projects the first field plane 307 with an imaging ratio of 100:1 onto the second field plane 309 . The numerical aperture NA in the second field plane 309 is 0.9. The diameter of the field in the second field plane 309 is 2 mm. The axial distance between the first field plane 307 and the second field plane 309 is 2389 mm.
The first partial objective 303 projects the first field plane 307 with an imaging ratio of 66:1 onto the intermediate image 311 . It includes the convex mirror 313 with the central mirror aperture 315 , and the concave mirror 317 with the central mirror aperture 319 . The concave mirror 317 is designed in such a way that the intermediate image 311 is formed in the vicinity of the convex mirror 313 . The axial distance between the mirror 317 and the paraxial position of the intermediate image 311 is equal to the axial distance between the mirror 317 and the mirror 313 and is 450.8 mm. The ratio of the diameter of the concave mirror 317 to the diameter of the convex mirror 313 is 14.9:1. The free optical working distance between the first field plane 307 and the mirror 317 is 1470 mm, assuming a substrate thickness of 33.3 mm on the optical axis OA for the mirror 317 .
The second partial objective 305 projects the intermediate image 311 onto the second field plane 309 with an imaging ratio of 1.5:1. The projection is performed via an intermediate projection of the intermediate image 311 onto the further intermediate image 343 . The intermediate image 311 is projected by the concave mirror 345 with the central mirror aperture 347 , and by the concave mirror 349 with the central mirror aperture 351 , onto the further intermediate image 343 which is projected, in turn, by the concave mirror 321 with the central mirror aperture 323 , and by the concave mirror 325 with the central mirror aperture 327 , onto the second field plane 309 .
The mirrors in the second partial objective 305 are respectively arranged in the vicinity of field planes. The optical power of the concave mirror 349 is designed in such a way that the further intermediate image 343 is formed in the vicinity of the concave mirror 345 . The axial distance between the mirror 349 and the paraxial position of the further intermediate image 343 is equal to the axial distance between the mirror 349 and the mirror 345 , and is 68.9 mm.
The concave mirrors 349 and 325 are arranged in the vicinity of the intermediate image 311 , or of the further intermediate image 343 . The axial distance between the concave mirror 349 and the intermediate image 311 is 18.9 mm, while that between the concave mirror 325 and the further intermediate image 343 is 37.5 mm. These axial distances also correspond in each case to the axial distances in relation to the mirror 313 , or to the mirror 345 . In the third exemplary embodiment, the axial distances between the mirrors 311 and 349 , or between the mirrors 345 and 325 , are smaller than the sum of the respective mirror substrates. Thus, by contrast with the second exemplary embodiment, the mirror 311 is located in the mirror aperture 351 of the mirror 349 , and the mirror 345 is located in the mirror aperture 327 of the mirror 325 . Whereas the mirror 349 determines the aperture obscuration in the second exemplary embodiment, the corresponding mirror 349 is no longer critical in the third exemplary embodiment. The substrate rear surfaces of the mirrors 313 , 349 and 345 are not plane. In order that the rays passing through the mirror apertures are not vignetted on the mirror substrates, the rear surfaces have frustoconical depressions surrounding the central mirror apertures.
The mirror 321 is arranged close to the second field plane 309 and has an axial distance of 40.0 mm from this plane. The mirror 321 has a diameter of 760.7 mm. Consequently, it should have a substrate thickness of at least 22.8 mm on the optical axis OA. The substrate thickness of the mirror 321 on the optical axis is 35 mm. The difference between the substrate thickness and the axial distance of the mirror 321 from the second field plane 309 represents the free optical working distance, which is 5.0 mm in the third exemplary embodiment. On the other hand, the mirror 321 is arranged so close to the second field plane 309 that the mirror obscuration of the mirror 321 is only 0.26 in the case of a numerical aperture NA=0.9 in the second field plane 309 .
The aperture plane 329 with the light blocking device 331 is located between the concave mirror 321 and the concave mirror 325 . The marginal rays 337 and 339 , which emanate from the two field points 333 and 335 in the first field plane 307 , go through the upper and lower margins of the aperture plane 329 . The field point 333 is located on the optical axis OA, and the field point 335 is located on the upper margin of the field at a distance of 100 mm from the optical axis OA. The aperture obscuration is 0.39 in the third exemplary embodiment. The ratio of the numerical aperture in the second field plane to the aperture obscuration is therefore 2.31. The mirror aperture 327 of the concave mirror 325 acts in a limiting fashion for the aperture obscuration in the third exemplary embodiment.
It was possible in the third exemplary embodiment largely to correct the field curvature by means of the negative optical power of the convex mirror 313 . The Petzval radius is 76472 mm.
It was possible in the third exemplary embodiment to correct the spherical aberration of third order to a value of 0.3 μm.
A lithographic projection exposure apparatus 453 for EUV lithography is illustrated schematically in FIG. 4 . A laser-induced plasma source 459 serves as light source. In this case, a Xenon target, for example, is excited by means of a pump laser 457 to emit EUV radiation. The illuminating system 455 includes the collector mirror 461 , the homogenizing and field-forming unit 463 and the field mirror 465 . Such illuminating systems are described, for example, in U.S. Pat. No. 6,198,793 (DE 199 03 807), which is owned by the same assignee as the present invention and whose content is incorporated herein by reference. The illuminating system 455 illuminates a restricted field on the micromirror array 467 , which is arranged on the holding and positioning unit 469 . The micromirror array 467 has 1000×1000 separately controllable mirrors of size 10 μm×10 μm. Taking account of a minimum distance of 0.5 μm between the micromirrors, the illuminating system 455 should illuminate a square field of size 10.5 mm×10.5 mm. The micromirror array 467 is located in the object plane of a projection objective 401 , which projects the illuminated field onto a photosensitive substrate 471 . The photosensitive substrate 471 is arranged on the holding and positioning unit 473 , which also permits scanning of the micromirror array 467 . One of the exemplary embodiments illustrated in FIGS. 1 to 3 can be used as projection objective 401 . The micromirror array 467 is arranged in the first field plane, and the photosensitive substrate 471 in the second field plane. In order for the field mirror 465 not to vignette the projecting beam path, the field mirror 465 must be arranged at a sufficiently large distance from the micromirror array 467 . On the other hand, this requires the illuminated field to be arranged not centered relative to the optical axis OA, but outside the optical axis. Since, however, the object fields of the exemplary embodiments shown have a diameter of 200 mm, the illuminated field can be arranged, for example, at a distance of 70 mm from the optical axis OA. The individual micromirrors of the micromirror array 467 are projected onto the photosensitive substrate 471 with an imaging ratio of 100:1, and so the images of the micromirrors have a size of 100 nm. Consequently, it is possible to produce structures with a resolution of approximately 100 nm on an image field of size 105 μm×105 μm, since the projection of the projection objective 401 is diffraction limited. By stepwise displacement and/or scanning of the photosensitive substrate 471 by means of the holding and positioning unit 473 , it is also possible to expose fields with dimensions of several millimeters. The lithographic projection exposure apparatus 453 also has the ray trap 475 . This absorbs the light rays of those ray pencils which are not aimed into the entrance pupil of the projection objective 401 by the micromirrors. The computer and control unit 477 is used to control the pump laser 457 , the illuminating system 455 , for the purpose of varying the pupil illumination, the controllable micromirror array 467 and the holding and positioning units 473 and 469 .
A further exemplary embodiment of a lithographic projection exposure apparatus 553 is illustrated in FIG. 5 . The lithographic projection exposure apparatus 553 has a reflective reticle 579 instead of the controllable micromirror array 467 . The elements in FIG. 5 which correspond to the elements of FIG. 4 have the same reference numerals as in FIG. 4 increased by the number 100. Reference may be made to the description relating to FIG. 4 for a description of these elements. Since the structures on the reflective reticle 579 can have dimensions of less than 1 μm, it is possible to produce structures with resolutions of less than approximately 10 nm on the photosensitive substrate 571 , since the projection of the projection objective 501 is diffraction limited.
An inspection system 681 for observing wafer surfaces is illustrated schematically in FIG. 6 . An excimer laser 685 which produces light with a wavelength of 157 nm serves as light source. The illuminating system 683 includes the homogenizing and field-forming unit 687 and the beam splitter 689 , for example a semitransparent mirror. The beam splitter 689 couples the illuminating light into the inspection objective 601 , which projects the surface of the object 691 to be analyzed onto the entry surface 693 of an observation unit 695 . The object 691 is arranged on an object stage 697 which permits the displacement and rotation of the object 691 . One of the exemplary embodiments illustrated in FIGS. 1 to 3 can be used as inspection objective 601 . The object 691 is arranged in the second field plane, and the entry surface 693 in the first field plane. It is possible, for example, to use the inspection objective 601 to analyze a surface of 500 μm×500 μm. The image corresponding to this object field has dimensions of 50 mm×50 mm on the entry surface 693 of the observation unit 695 . The computer and control unit 699 is used to control the light source 685 , the illuminating system 687 , for the purpose of varying the pupil illumination, and the object stage 697 , and to evaluate the measured data from the observation unit 695 . Using an inspection objective in accordance with the exemplary embodiments 1 to 3 has the advantage that it is possible by means of an appropriate coating of the mirrors to adapt the inspection objective to any wavelength, or to a wide wavelength range. In particular, the inspection objective can also be used at EUV wavelengths of less than 20 nm.
TABLE 1
Optical Data for Objective of FIG. 1A/1B
Element
Curvature Radius
Aperture Diameter
(Ref. Symbol)
Front
Back
Thickness
Front
Back
Glass
Object
inf.
1684.0346
Mirror 1 (13)
A(1)
−68.8152
C-1
reflecting
Mirror 2 (17)
A(2)
344.7808
C-2
reflecting
Mirror 3 (21)
A(3)
−62.6453
C-3
reflecting
APERTURE STOP
338.9074
−142.0994
Mirror 4 (25)
A(4)
204.7447
C-4
reflecting
80.2169
Image
Image Distance =
39.9998
2.0029
inf.
APERTURE DATA
Diameter
Decenter
Aperture
Shape
X
Y
X
Y
Rotation
C-1
Circle
(obsc.)
25.069
Circle
6.000
6.000
C-2
Circle
(obsc.)
76.190
Circle
34.000
34.000
C-3
Circle
(obsc.)
315.840
Circle
90.000
90.000
C-4
Circle
(obsc.)
388.014
Circle
100.000
100.000
Aspheric Constants
Z
=
(
curv
)
Y
2
1
+
[
1
(
1
+
K
)
(
curv
)
2
Y
2
]
1
2
+
(
A
)
Y
4
+
(
B
)
Y
6
+
(
C
)
Y
8
+
(
D
)
Y
10
+
(
E
)
Y
12
+
(
F
)
Y
14
+
(
G
)
Y
16
+
(
H
)
Y
18
+
(
J
)
Y
20
K
A
B
C
D
aspheric
curv
E
F
G
H
J
A(1)
0.01632142
0.721125
−1.13241E−06
−7.44173E−10
−1.20959E−13
1.82841E−16
5.01736E−33
2.59205E−34
0.00000E+00
0.00000E+00
0.00000E+00
A(2)
0.01249319
0.374720–
−1.34649E−07
−2.20696E−11
−3.87070E−15
−5.51394E−19
7.61820E−23
−4.74274E−26
0.00000E+00
0.00000E+00
0.00000E+00
A(3)
−0.0016322
−8.138119–
3.08966E−10
8.83050E−14
1.52159E−20
1.03323E−23
8.43173E−29
2.01064E−33
0.00000E+00
0.00000E+00
0.00000E+00
A(4)
0.00220115
1.243485
4.66665E−10
−4.05558E−15
4.03013E−20
−5.94690E−25
6.74937E−30
−3.83976E−35
0.00000E+00
0.00000E+00
0.00000E+00
AT USED CONJUGATES:
REDUCTION =
OBJECT DIST =
TOTAL TRACK =
IMAGE DIST =
OAL =
−0.0100
1684.0346
2000.0000
39.9998
275.9656
TABLE 2
Optical Data for Objective of FIGS. 2A/2B
Curvature
Aperture
Element
Radius
Diameter
(Ref. Symbol)
Front
Back
Thickness
Front
Back
Glass
Object
inf.
1533.8845
Mirror 1 (213)
A(1)
−447.4711
C-1
reflecting
Mirror 2 (217)
A(2)
558.0315
C-2
reflecting
Mirror 3 (245)
A(3)
−60.5605
C-3
reflecting
Mirror 4 (249)
A(4)
376.0924
C-4
reflecting
Mirror 5 (221)
A(5)
−130.5321
C-5
reflecting
APERTURE STOP
748.0479
−135.0000
Mirror 6 (225)
A(6)
265.5321
C-6
reflecting
Image Distance =
40.0232
166.8325
Image
inf.
2.0046
APERTURE DATA
Diameter
Decenter
Aperture
Shape
X
Y
X
Y
Rotation
C-1
Circle
(obsc.)
29.950
Circle
6.000
6.000
C-2
Circle
(obsc.)
432.760
Circle
90.000
90.000
C-3
Circle
(obsc.)
115.248
Circle
10.000
10.000
C-4
Circle
(obsc.)
136.401
Circle
60.000
60.000
C-5
Circle
(obsc.)
748.249
Circle
200.000
200.000
C-6
Circle
(obsc.)
748.006
Circle
240.000
240.000
Aspheric Constants
aspheric
curv
K
A
B
C
D
A(1)
0.01462135
4.236799
0.00000E+00
−2.34672E−10
2.25315E−13
0.00000E+00
A(2)
0.00215389
0.031898
0.00000E+00
1.71983E−16
4.27637E−21
0.00000E+00
A(3)
−0.00076244
381.118675
0.00000E+00
−2.25582E−12
−7.14313E−16
0.00000E+00
A(4)
0.00849256
0.414914
0.00000E+00
1.39628E−13
−3.22627E−17
0.00000E+00
A(5)
−0.00146641
−0.715112
0.00000E+00
−2.04954E−16
−6.04643E−22
0.00000E+00
A(6)
0.00185791
−1.171636
0.00000E+00
−1.34911E−15
1.97533E−21
0.00000E+00
AT USED CONJUGATES:
REDUCTION =
OBJECT DIST =
TOTAL TRACK =
IMAGE DIST =
OAL =
0.0100
1533.8845
2000.0000
40.0232
426.0923
TABLE 3
Optical Data for Objective of FIGS. 3A/3B
Curvature
Aperture
Element
Radius
Diameter
(Ref. Symbol)
Front
Back
Thickness
Front
Back
Glass
Object
inf.
1954.1364
Mirror 1 (313)
A(1)
−450.8028
C-1
reflecting
Mirror 2 (317)
A(2)
538.6037
C-2
reflecting
Mirror 3 (345)
A(3)
−68.8878
C-3
reflecting
Mirror 4 (349)
A(4)
375.9476
C-4
reflecting
Mirror 5 (321)
A(5)
−134.5548
C-5
reflecting
APERTURE STOP
759.6775
−135.0000
Mirror 6 (325)
A(6)
269.5548
C-6
reflecting
Image Distance =
40.0005
166.7569
Image
inf.
2.0027
Diameter
Decenter
Aperture
Shape
X
Y
X
Y
Rotation
C-1
Circle
(obsc.)
36.788
Circle
4.000
4.000
C-2
Circle
(obsc.)
550.616
Circle
80.000
80.000
C-3
Circle
(obsc.)
126.324
Circle
4.000
4.000
C-4
Circle
(obsc.)
156.779
Circle
40.000
40.000
C-5
Circle
(obsc.)
760.748
Circle
200.000
200.000
C-6
Circle
(obsc.)
759.241
Circle
200.000
200.000
Aspheric Constants
aspheric
curv
K/E
A/F
B/G
C/H
D/J
A(1)
0.01453296
3.993966
−1.25979E−07
−2.40984E−10
−2.22973E−13
−1.92806E−16
0.00000E+00
0.00000E+00
0.00000E+00
0.00000E+00
0.00000E+00
0.00000E+00
A(2)
0.00214496
−0.072178
9.97447E−11
5.58371E−16
2.94983E−21
2.11781E−27
1.14313E−31
1.09251E−37
0.00000E+00
0.00000E+00
0.00000E+00
A(3)
−0.00095338
177.846664
−4.27020E−08
3.95468E−12
3.32517E−20
−6.96347E−20
1.24958E−24
9.52941E−28
0.00000E+00
0.00000E+00
0.00000E+00
A(4)
0.00808626
0.279920
5.46076E−09
3.59983E−13
5.29416E−18
−6.95655E−23
1.93949E−25
2.44723E−30
0.00000E+00
0.00000E+00
0.00000E+00
A(5)
−0.00151095
−0.696060
0.00000E+00
−3.66210E−16
−3.54668E−22
−1.33788E−27
−2.47308E−33
−1.25578E−38
0.00000E+00
0.00000E+00
0.00000E+00
A(6)
0.00185048
−1.256318
−1.93114E−11
−1.38066E−15
2.59583E−21
−5.18058E−27
7.48520E−33
6.54710E−39
0.00000E+00
0.00000E+00
0.00000E+00
AT USED CONJUGATES:
REDUCTION =
OBJECT DIST =
TOTAL TRACK =
IMAGE DIST =
OAL =
0.0100
1954.1364
2388.9976
40.0005
394.8606
|
In accordance with the present invention, a projection exposure apparatus includes an illuminating system to illuminate a drivable micromirror array and an objective which projects the drivable micromirror array onto the photosensitive substrate. The objective includes mirrors which are arranged coaxial with respect to a common optical axis. The objective can be a catoptric objective and can have a numerical aperture at the substrate greater than 0.1 and can have an imaging scale ratio of greater than 20:1. The objective can also include at least two partial objectives with an intermediate image plane between the at least two partial objectives and can consist of mirrors that are coated with reflecting layers which are adapted to reflect two mutually separated operating wavelengths.
| 6
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This application is related to the following U.S. patent applications: U.S. patent application Ser. No. 08,990,246 entitled “Web Interface and Method for Displaying Directory Information,” filed Dec. 15, 1997, now U.S. Pat. No. 6,195,666; U.S. patent application Ser. No. 08/990,992, entitled “Web Interface and Method for Accessing and Displaying Directory Information,” filed Dec. 15, 1997, and U.S. patent application Ser. No. 08/990,519, entitled “System and Method for Creating a Search Form for Accessing Directory Information,” filed Dec. 15, 1997, now U.S. Pat. No. 6,192,362.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to an electronic messaging system and more particularly relates to World Wide Web (“Web”) interface and method for displaying directory information.
2. Description of the Background
Electronic directories are evolving into important information tools having a myriad of applications. They operate much like a printed directory; that is, they provide names, locations and other information about people, products, equipment and organizations. First generation electronic directories were designed for a particular application, such as an employee or e-mail system directory, and thus had limited usefulness outside the scope of the application. However, the growth of local area networks (LANs), heterogeneous e-mail networks, the Internet, and other electronic communications media such as telephone and fax has resulted in enterprises having to manage a hodgepodge of proprietary directory systems. These directory systems rarely interoperate, are costly to maintain, and frequently contain redundant information. Enterprises today are finding a need to unify these disparate directories with a single standards-based directory to reduce maintenance costs and provide universal access through well-defined interfaces. Most directory vendors have chosen X.500 as the technology best suited to meet this need.
Until recently, users could only access information contained in an X.500 directory through specialized applications called directory user agents (DUAs). DUAs were typically limited in functionality, because (a) they were tailored for particular X.500 implementations, making them unable to interoperate with other X.500 directories; and ( b ) they typically displayed directory information in a fixed format, with little if any ability to customize the presentation of data.
Another shortcoming of existing directory access systems is that they fail to provide users with access to directory information via a World Wide Web (“Web”) interface in a configurable manner. Neither the format in which the information is published nor the particular content of the information is customizable. The end result therefore looks the same for any user requesting the information, irrespective of whether the user is linked via an internal network, such as a corporate intranet, or via an external network, such as the Internet. Moreover, the location or identification of the user does not affect the type of information that is provided. This may result in the disclosure of personal or otherwise secure information (such as a home telephone number) to unintended recipients.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to overcome these and other drawbacks of existing systems.
It is another object of the invention to provide a request mapper for linking a directory entry to a template file in response to a directory request.
It is another object of the present invention to provide a friendly name mapper for correlating an abbreviated name to a non-abbreviated name.
It is another object of the invention for these mappers to be configurable by an administrator.
According to one embodiment of the present invention, these and other objects and technical advantages of the invention are achieved by providing a web interface for accessing directory information. The Web interface for accessing directory information comprises a request mapper that links directory data to a template file in response to a directory request, and a friendly name mapper that correlates an abbreviated name to a non-abbreviated name, wherein said abbreviated name refers to at least one entry of said directory data.
In another embodiment, a method for accessing directory information in accordance with the invention comprises the following steps: (1) receiving a request for directory data; (2) determining whether the request is a distinguished name request, wherein the distinguished name request is a request for a distinguished name; (3) in response to a determination that the request is not a distinguished name request, retrieving a directory resource corresponding to the request; (4) in response to a determination that the request is a distinguished name request, determining whether the distinguished name is mapped; (5) in response to a determination that the distinguished name is not mapped, retrieving an object class of the distinguished name and finding a template using the object class; and (6) in response to a determination that the distinguished name is mapped, finding a template using the distinguished name.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the present invention, and the objects and advantages thereof, reference is now made to the following descriptions taken in connection with the accompanying drawings in which:
FIG. 1 is a block diagram of a Web interface system.
FIG. 2 is a block diagram of a Web interface system including a preferred embodiment of the Web to X.500 gateway.
FIG. 3 is a flow chart illustrating the steps for displaying information according to a preferred embodiment of the invention.
FIG. 4 is a flow chart illustrating the steps for request processing.
FIG. 5 illustrates an example of Read request mapping.
FIG. 6 illustrates an example of List request mapping.
FIG. 7 illustrates an example of Search request mapping.
FIG. 8 illustrates the layout of a template file.
FIGS. 9 ( a ) and 9 ( b ) illustrate a read template file and the corresponding read request output, respectively.
FIGS. 10 ( a ) and 10 ( b ) illustrate a simple list template file and the corresponding simple list request output, respectively.
FIGS. 11 ( a ) and 11 ( b ) illustrate a complex list template file and the corresponding complex list request output, respectively.
FIGS. 12 ( a ) and 12 ( b ) illustrate a search template file and the corresponding search request output, respectively.
FIG. 13 ( a ) illustrates a first example of a search form HTML.
FIG. 13 ( b ) illustrates a second example of a search form HTML.
FIG. 13 ( c ) illustrates a search form output for the examples of FIGS. 13 ( a ) or 13 ( b ).
FIG. 14 ( a ) illustrates a third example of a search form HTML.
FIG. 14 ( b ) illustrates a search form output corresponding to FIG. 13 ( a ).
FIG. 14 ( c ) illustrates a search request output corresponding to FIGS. 14 ( a ) and 14 ( b ).
FIG. 15 ( a ) illustrates a fourth example of a search form HTML.
FIG. 15 ( b ) illustrates a search form output corresponding to FIG. 15 ( a ).
FIG. 15 ( c ) illustrates a search request output corresponding to FIGS. 15 ( a ) and 15 ( b ).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred embodiment of the present invention and its advantages are best understood by referring to FIGS. 1 through 15 ( c ) of the drawings, like numerals being used for like and corresponding parts of the various drawings.
Referring to FIG. 1, which is a block diagram of a Web interface system, X.500 Distributed System Agent (DSA) 104 is the database in which directory information is stored. Such information may include employees' photographs, phone numbers, product catalogs and the like. DSA 104 communicates with LDAP server 102 . In a preferred embodiment, the protocol used in this communication is directory access protocol (DAP). LDAP server 102 is linked to the Web to X.500 gateway 100 , which converts an HTTP request into an LDAP request, and vice versa. The Web to X.500 gateway 100 may be further coupled with administrative interface 106 , which permits access by an administrator, and Web browser 108 , which permits access by a user. Using the Web browser 108 , a user can access information about people, products and resources in scalable, robust, secure messaging directories (such as X.500 directories), and can publish multiple views of such information. This information can be on an internal network for enterprise use or on a public network accessible by various individuals, organizations and the like.
The Web to X.500 gateway 100 provides a user-friendly way to publish enterprise directory information. Administrators can easily publish directory information that users can access, search and view from Web browsers, LDAP-enabled clients and X.500-based applications. The Web to X.500 gateway 100 allows administrators to easily define data mappings and conversions from a wide variety of data sources, thereby integrating multi-sourced content into a directory.
FIG. 2 illustrates the topology of a preferred embodiment of Web to X.500 gateway 100 . The Web to X.500 gateway 100 includes a server (such as a Web server) 200 , which accepts requests for directory information; request processor 202 , which responds to the requests; map 212 , which correlates the requests to template files (i.e., request mapping) and correlates abbreviated names to unabbreviated names (i.e., friendly name mapping); and template files 214 , which contain templates that dynamically control the publishing of the requested directory information. A user may access the server 200 via Web Browser 108 through Sockets Application Programming Interface (Sockets API) 204 . Additionally, an administrator controls and configures the server 200 via Server Control and Configuration system 218 .
In order to update and build the map and template files, a map build process 210 and a template build process 208 are used. Map build 210 creates and updates map 212 , while template build 208 creates and updates template files 214 . The administrator, via Administrator Interface 106 , is responsible for the map build process 210 and template build process 208 . Map 212 can correlate an abbreviated name to a non-abbreviated name. Map 212 can also correlate a request to a template 214 .
The request processor 202 communicates with the LDAP Application Programming Interface (API) 206 in order to access information through the LDAP Server 102 from the X.500 DSA 104 .
The server 200 maintains communication with Web clients such as Web browsers 108 . The server 200 to Web browser 108 communication is based on the request-response model of client/server communication. That is, the client sends a request to the server and the server responds. Generally, the client is requesting a resource that the server will provide. In the case of the Web server/browser communication, the protocol used is HTTP.
Pursuant to the HTTP protocol, the Web browser 108 establishes a connection with the server 200 and sends a request to the server 200 . This request contains a request method, a Uniform Resource Locator (URL) and a message containing additional information. The request method can be GET, which retrieves data specified in the URL, or POST, which sends information to the server for further action. The URL specifies a resource accessible by the server. The message contains request modifiers, client information, and possibly a body of data. The body of data contains information that the server will use for further action.
The server 200 responds with a status code and a message containing additional information. The status code may be: OK; a bad request has occurred; an internal server error has occurred; the request method is not implemented by the server; or the server is unavailable. The message contains server information, resource information and possibly a body of data. The body of data contains the resource that was requested or an error message.
The request processor 202 provides the output to the end user. The server 200 starts the request processing and returns to its event-driven loop. A preferred embodiment of the invention handles a plurality of requests, including retrieve resource, Read distinguished name (“DN”), List distinguished name and Search distinguished name.
To process a retrieve resource request, the gateway expects a GET from the client with the URL in the form “path and name of resource.” The resource may be an image or static document accessible by the server. The gateway responds with this resource.
To process a read distinguished name (Read) request, the client sends a GET with a URL in the form “Distinguished name.” The gateway processes a Read as a single entry read of the DN.
To process the list distinguished name (List) request, the client sends a GET with a URL in the form “Distinguished name?” The gateway processes a List as a single entry read of the DN and a one level list of the DN.
To process the search distinguished name request (Search), the client sends a POST with a URL in the form: “Distinguished name”?“?Search format”. The gateway processes a Search as a single entry read of the DN and a full sub-tree search of the DN.
FIG. 3 illustrates the steps for displaying directory information, according to a preferred embodiment of the invention. In step 300 , the server accepts at least one information request from a Web browser. In step 302 , the server retrieves at least one entry from a directory responding to the information request. In step 304 , the map correlates the entry with a template file to create a response, the template file including predetermined criteria for controlling the display of the entry. In step 306 , the response is published according to predetermined criteria. The response may be published by the request processor 202 to a user via a public network, such as the Internet, or a private network, such as a corporate intranet.
The map 212 is used during request processing to link one object to another. There are two types of mappings used in request processing: request mappings and friendly name mappings. Request mappings are used during request processing to determine which template file should be used. The request mappings link a portion of the X.500 directory to a template file. Request mappings include Read request mappings, List request mappings and Search request mappings.
A specific mapping belonging to the Read, List or Search set may be one or two entity specific types: distinguished name (DN) and/or object class (OC). A distinguished name request mapping correlates a specific DN to a template file. If a request of the specified operation type occurs for this specific DN, then this mapping is used. An object class request mapping correlates all DNs of a specific object class to a template file. If a request of the specified operation type occurs for a DN with this specific OC, then this mapping is used. A distinguished name request mapping preferably always overrides an object class request mapping.
FIG. 4 illustrates the steps for request processing in more detail. First, it is determined whether the request is for a DN 402 . If the request is not for a DN, the requested resource is read 404 . If the request is for a DN, it is determined whether the DN is mapped 406 . If the DN is not mapped, the object class of the DN is retrieved from the X.500 directory via LDAP 408 and this OC is used to find a template, assuming the OC is mapped 412 . If the OC is not mapped, an appropriate error message is used 410 . If the DN is mapped, the DN is used to find a template 412 . If a template is found and the request is a Read or List request, the tags of the template are filled in via LDAP 414 . If the template is found and the request is a Search request, a search filter is created from the input data and the search format. The template is then filled in via LDAP 414 . If the template is not found, an appropriate error message is used 410 . A response is sent to the browser 416 .
In the following description, ocfile.html and dnfile.html are used as filename examples. In practice, the filenames would be more descriptive and different for each request mapping type.
Read request mapping is used when a Read request is received. A Read request mapping links a portion or multiple portions of the X.500 directory to a specific template file. Referring now to FIG. 5, which illustrates an example of Read request mapping, the relationship between a Read request mapping, the X.500 directory and a template file can be seen. This example shows both DN and OC request mappings.
For the DN request mapping 502 , a single portion of the X.500 directory is mapped. The entry o=XYZCorp,c=US is mapped to the template file dnfile.html 504 . The file dnfile.html 504 includes a template for the organization object class. A response based on dnfile.html is created for a Read request of o=XYZCorp,c=US.
For the OC request mapping 506 , multiple portions of the X.500 directory are mapped. For example, the object class organization is mapped to the template file ocfile.html 508 . The file ocfile.html 508 includes a template for the organization object class. A response based on ocfile.html is created for a Read request of any organization.
List request mappings are used when a List request is received. A List request mapping links a portion or multiple portions of the directory to a specific template file. Referring now to FIG. 6, which illustrates an example of List request mapping, the relationship between a List request mapping, the X.500 directory and a template file can be seen. This example shows both DN and OC request mappings.
For the DN request mapping 602 , a single portion of the X.500 directory is mapped. The entry o=XYZCorp,c=US is mapped to the template file dnfile.html 604 .
The file dnfile.html 604 includes tags for the organization object class and a template for the organizationalUnit object class and any other immediate subordinate object class. A response based on dnfile.html is created for a List request of o=XYZCorp,c=US.
For the OC request mapping 606 , multiple portions of the X.500 directory are mapped. For example, the object class organization is mapped to the template file ocfile.html 608 . The file ocfile.html 608 includes tags for the organization object class and a template for the organizationalUnit object class and any other immediate subordinate object class. A response based on ocfile.html is created for a List request of any organization.
Search Request mappings are used when a Search request is received. A request mapping that is a member of this set links a portion of the directory (or multiple portions) to a specific template file. Referring now to FIG. 7, which illustrates an example of Search request mapping, the relationship between a search request mapping, the X.500 directory and a template file can be seen. This example shows both DN and OC request mappings.
For the DN request mapping 702 , a single portion of the X.500 directory is mapped. The entry o=XYZCorp,c=US is mapped to the template file dnfile.html. The file dnfile.html 704 includes tags for the organization object class, a template for the organizationalUnit object class, a template for the person object class and any other object class in the full sub-tree. A response based on dnfile.html is created for a Search request of o=XYZCorp,c=US.
For the OC request mapping 706 , multiple portions of the directory are mapped. The object class organization is mapped to the template file ocfile.html. The file ocfile.html 708 includes tags for the organization object class, a template for the organizationalUnit object class, a template for the person object class, and any other object class in the full sub-tree. A response based on ocfile.html is created for a Search request of any organization.
Friendly name mappings are used during request processing to replace abbreviated names with more easily understood names. Two types of friendly name mappings are attribute mappings and country mappings. Attribute mappings are used during request processing to replace (in a response) the X.500 directory attributes with the full name of the attribute. An example of attribute mapping is using “cn” for “Common Name.” Country mappings are used during request processing to replace (in a response) returned country names with the full name of the country. Some examples of country mappings are “AR” for “Argentina,” “CA” for “Canada,” and “US” for “United States.”
Any of the mappings, including read request mappings, list request mappings, search request mappings, attribute mappings and country mappings, may be configured by the administrator. Mapping administration preferably is based on schema and directory information. Attribute mappings should be maintained for all attributes within the directory that will be displayed. Country mappings should be maintained for all countries within the directory that will be displayed. Request mappings should be maintained for every object class that a request will be executed. Each of those request mappings requires a template file to fulfill the request. In the event that a response will look different for a specific entry, a distinguished name request mapping must be maintained.
The template files 210 are used in request processing to create a response. Files include non-template files and template files. Non-template files are any files that act as a gateway response to a retrieve resource request. Examples of non-template files are standard HTML files and image files.
Template files are the files that are used to dynamically build responses for Read, List or Search requests. FIG. 8 illustrates a layout of a template file. Template files include general text 802 and templates 804 . The general text sections 802 of the template files include HTML codes and special gateway tags, and do not correspond to a specific object class. The general text sections 802 are preferably always displayed and any gateway tags present are filled with data from the DN in the request. The template sections 804 of the template file include HTML codes and special gateway tags. A template 804 defines a section of the template file that is for a specific object class. A template section 804 is preferably only displayed if it corresponds to an object class that is present in the Read, list or Search request.
The gateway tags include TEMPLATE, DN, UPLEVEL, ATTR, VAL, LINK and LOOP. The TEMPLATE tag indicates to the gateway that a template for an object class is being defined. The template may contain any HTML codes in addition to the other gateway tags. A single HTML file may contain any number of templates. Any templates that are not used will be ignored and discarded in the HTML output. The format of the TEMPLATE tag is: %TEMPLATE OC=“objectClass” [options]% % /TEMPLATE%. The string objectClass indicates which object class is to be used for the template. The tag % /TEMPLATE% indicates the end of the template to the gateway. One option is the DISPLAY option, which controls how many values are displayed for a List or Search request. The DISPLAY option may be ONE or ALL. If the DISPLAY option is not present, the template defaults to DISPLAY=“ALL”. If the ONE option is specified, only the first value found appears in the list.
The DN tag indicates to the gateway that the current distinguished name should be substituted. The format of the DN tag is % DN [options]%. If no options are present, the relative distinguished names (RDNs) are separated by commas. The option PRETEXT=“text” places text before each RDN. The option POSTTEXT=“text” appends text after each RDN. The option DELIMIT=“text” places text between each RDN. In a Read template file, the current DN is defined as the DN in the Read request. In a List or Search template file, the definition depends on the position of the DN tag in the file. If the DN tag is located in the general text section, it is defined as the DN in the List or Search request. If the DN tag is inside a loop, it is defined as the current DN that has been returned by the List or Search request from the X.500 directory.
The UPLEVEL tag generates a hyperlink to a List request on the parent DN of the current DN. The format of the UPLEVEL tag is %UPLEVEL%[text/tags] %/UPLEVEL%. [text/tags] may be any valid HTML and/or the gateway tags ATTR or VAL. The UPLEVEL tag acts like the <A HREF=“”></A>HTML control code. Using the enclosed text, it creates a hyperlink to a List request on the parent DN of the current DN.
The ATTR tag replaces in the response the abbreviated X.500 attribute with the friendly name from the attribute mappings. The format of the ATTR tag is %ATTR NAME=“name”%. The string name indicates which X.500 attribute mapping to use. If no mapping is found, the abbreviated X.500 attribute is used. This is a text replacement function.
The VAL tag retrieves the values of an X.500 attribute and places them in the HTML document. The format of the VAL tag is %VAL NAME=“name”%. The string name indicates which X.500 attribute to retrieve.
The LOOP tag is used to specify that a portion of a template should be repeated for all corresponding DNs. The format of a LOOP tag is: %LOOP[options]%[loop text]% /LOOP%. The option SPLIT=“number” indicates that the returned list should be split into “number” of segments. The option SEGMENT=“number” indicates the segment that should be processed in this loop. The text may contain any valid HTML and the gateway tags LINK, ATTR, VAL or DN. LOOP tags may be used in List and Search templates.
The LINK tag acts like the <A HREF=“”></A>HTML control code. Using the enclosed text, it creates a hyperlink of a Read request of the current DN. This tag is generally used in a LOOP for a Search or List request, creating links to the DNs listed. The format of a LINK tag is: %LINK% [text/tags] % / LINK%. [text/tags] may be any valid HTML and/or the gateway tags ATTR or VAL.
Template files combine HTML codes with the special gateway tags to allow the display of information from an X.500 directory. A Read template file is used to display data about one specific X.500 directory entry. To process a Read request, the gateway expects a GET from the client with the URL in the form: “Distinguished name”. A template should be defined in the template file for the object class of the Read DN. When the template file is processed, any object class that defines the DN will be processed and displayed. A Read template file may include the following tags in its general text or template file: ATTR (X.500 attribute), VAL (X.500 value), DN (current distinguished name), UPLEVEL (hyperlink to List parent DN) and LINK (hyperlink to Read current DN).
FIGS. 9 ( a ) and 9 ( b ) illustrate a read template file and the corresponding read request output, respectively. The read request output may be in any number of formats, including the one illustrated in FIG. 9 ( b ). Given the template file illustrated in FIG. 9 ( a ), and the Read request of http://127.0.0.1:8888/ou%3dSALES%2co%3dXYZCorp% 2cc%3dUS , the response would be that illustrated in FIG. 9 ( b ). Based on directory information, the %DN% 902 following the <TITLE> 904 is replaced with ou=SALES,o=XYZCORP,c=US. The %TEMPLATE OC=“organizationalUnit”% 906 and %/TEMPLATE% 908 define a template section for the organizationalUnit object class. Based on attribute mappings, the %ATTR NAME%=“ou”% 910 is replaced with Organizational Unit. Based on directory information, the %DN% 912 is replaced with ou=SALES,o=XYZCORP,c=US. Based on directory information, the %val name=“ou”% 914 is replaced with SALES. The resulting text (<A HREF=“ou=SALES,o=XYZCORP, c=US?”>SALES</A>) is displayed by the browser as a hyperlink to list SALES.
Based on attribute mappings, the %ATTR NAME=“sa”% 916 is replaced with Street Address. Based on directory information, the %VAL NAME=“sa”% 918 is replaced with 1 XYZCorp Way. Based on attribute mappings, the %ATTR NAME=“l ”% 920 is replaced with Location. Based on directory information, the %VAL NAME=“l”% 922 is replaced with Anywhere. Based on attribute mappings, the %ATTR NAME=“sopn”% 924 is replaced with State or Province. Based on directory information, the %VAL NAME=“sopn”% 926 is replaced with XX. Finally, the %UPLEVEL% 928 and the %/UPLEVEL% 930 define an uplevel section. Based on directory information, the result of the uplevel section (<A HREF=“o=XYZCORP,c=US?”>Up to XYZCORP</A>) is displayed by the browser as a link to list XYZCorp.
A List template file displays information for an X.500 directory entry and those entries one level below the entry. To process the List request, the gateway expects a GET from the client with the URL in the form: “Distinguished name”?
A template is preferably defined in the template file for each object class that may be used to display directory entries under the distinguished name. Tags are placed in the general text section for the DN to List. The gateway tags that may be used in the general text or template of the List template file include ATTR (X.500 attribute), VAL (X.500 value), DN (current distinguished name), UPLEVEL (hyperlink to List parent DN) and LINK (hyperlink to Read current DN). LOOP, which causes the gateway to loop through all the DNs that correspond to the template, may be used in the template of the List template file.
FIGS. 10 ( a ) and 10 ( b ) illustrate a simple list template file and the corresponding simple list request output, respectively. Given the template file illustrated in FIG. 10 ( a ), and the List request http://127.0.0.1:8888/ou%3dSALES%2co%3d XYZCorp%2cc%3dUS?, the response would be that illustrated in FIG. 10 ( b ). Based on directory information, the %DN% 1002 is replaced with ou=SALES,o=XYZCORP,c=US. Based on attribute mappings, the %ATTR NAME=“ou”% 1004 is replaced with Organizational Unit. Based on directory information, the %VAL NAME=“ou”% 1006 is replaced with SALES. The %TEMPLATE OC=“pilotPerson”% 1008 and %/TEMPLATE% 1010 define a template section for the pilotPerson object class. The %LOOP% 1012 and %/LOOP% 1014 define a loop section that will be repeated for every pilotPerson found in the directory.
The following refers to the first pilotPerson found in the directory. Based on attribute mappings, the %ATTR NAME=“cn”% 1016 is replaced with Common Name. The %LINK% 1018 and %/LINK% 1020 defines a link section for the current pilotPerson. Based on directory information, the %VAL NAME=“cn”% 1022 is replaced with John Doe. The result of the link section (<A HREF=“cn=JOHN DOE, ou=SALES, o=XYZCORP,c=US”>John Doe</A>) is displayed by the browser as a link to read John Doe (see FIG. 10 ( b )). Based on attribute mappings, the %ATTR NAME=“t”% 1024 is replaced with Title. Based on directory information, the %VAL NAME=“t”% 1026 is replaced with Salesman. The LOOP is now repeated for the next pilotPerson found in the directory. Based on attribute mappings, the %ATTR NAME=“cn”% 1016 is replaced with Common Name. The %LINK% 1018 and %/LINK% 1020 defines a link section for the current pilotPerson. Based on directory information, the %VAL NAME=“cn”% 1022 is replaced with Jane Doe. The result of the link section (<A HREF=“cn=JANE DOE,ou=SALES,o=XYZCORP,c=US”>Jane Doe</A>) is displayed by the browser as a link to read Jane Doe (see FIG. 10 ( b )). Based on attribute mappings, the %ATTR NAME=“t”% 1024 is replaced with Title. Based on directory information, the %VAL NAME=“t”% 1026 is replaced with Manager. The %UPLEVEL% 1028 and %/UPLEVEL% 1030 define an uplevel section. Based on directory information, the result of the uplevel section (<A HREF=“o=XYZCORP, c=US?”>Up to XYZCorp</A>) is displayed by the browser as a link to list XYZ Corp (see FIG. 10 ( b )).
FIGS. 11 ( a ) and 11 ( b ) illustrate a complex list template file and the corresponding list request output, respectively. Given the template file illustrated in FIG. 11 ( a ), and the List request http://127.0.0. 1:888/ou3dSALES%2co%3dXYZ Corp%2cc%3dUS?, the response would be that illustrated in FIG. 1 l( b ). Based on directory information, the %DN% 1102 is replaced with ou=SALES, o=XYZCORP, c=US. Based on directory information, the %DN DELIMIT=“<BR>”PRETEXT=“<STRONG>”POSTTEXT=“</STRONG>% 1104 is replaced with <STRONG>ou=SALES</STRONG><BR><STRONG>o=XYZCORP</STRONG><BR><STRONG>c=US </STRONG>. Based on attribute mappings, the %ATTR NAME=“ou”% 1106 is replaced with Organizational Unit. Based on directory information, the %VAL NAME=“ou”PRETEXT=“<STRONG>”POSTTEXT=</STRONG>“% 1108 is replaced with <STRONG>SALES</STRONG>. Based on attribute mappings, the %ATTR NAME=“sa”% 1110 is replaced with Street Address. Based on directory information, the %VAL NAME=“sa”% 1112 is replaced with 1 XYZCorp Way. Based on attribute mappings, the %ATTR NAME=“l”% 1114 is replaced with Location. Based on directory information, the %VAL NAME=“l”% 1116 is replaced with Anywhere. Based on attribute mappings, the %ATTR NAME=“sopn ”% 1118 is replaced with State or Province. Based on directory information, the % VAL NAME=“sopn”% 1120 is replaced with XX. Based on attribute mappings, the %ATTR NAME=“d”% 1122 is replaced with Description. Based on directory information, the %VAL NAME=“d”POSTTEXT=“</LI>”PRETEXT=“<LI>”% 1124 is replaced with <LI>With X 500 Directory emphasis </LI><LI>The sales unit</LI><LI>Specializing in messaging services</LI>. The %TEMPLATE OC=“pilotPerson”% 1126 and %/TEMPLATE% 1128 define a template section for the pilotPerson object class. The %LOOP% 1130 and %/LOOP% 1132 define a loop section to be repeated for every pilotPerson found in the directory.
The following refers to the first pilotPerson found in the directory. The %LINK% 1134 and %/LINK% 1136 defines a link section for the current pilotPerson. Based on directory information, the % VAL NAME=“cn ”% 1138 is replaced with John Doe. The result of the link section (<A HREF=“cn=JOHN DOE, ou=SALES, o=XYZCORP,c=US”>John Doe</A>) is displayed by the browser as a link to read John Doe. Based on directory information, the %VAL NAME=“t”% 1140 is replaced with Salesman.
The following refers to the second pilotPerson found in the directory. The %LINK% 1134 and %/LINK% 1136 defines a link section for the current pilotPerson. Based on directory information, the % VAL NAME=“cn”% 1138 is replaced with Jane Doe. The result of the link section (<A HREF=“cn=JANE DOE,ou=SALES,o=XYZCORP, c=US”>Jane Doe</A>) is displayed by the browser as a link to read Jane Doe. Based on directory information, the % VAL NAME=“t”% 1140 is replaced with Manager.
The following refers to the third pilotPerson found in the directory. The %LINK% 1134 and %/LINK% 1136 defines a link section for the current pilotPerson. Based on directory information, the % VAL NAME=“cn”% 1138 is replaced with John Public. The result of the link section (<A HREF=“cn=JOHN PUBLIC,ou=SALES,o=XYZCORP, c=US”>John Public</A>) is displayed by the browser as a link to read John Public. Based on directory information, the %VAL NAME=“t”% 1140 is replaced with Receptionist.
The %TEMPLATE OC=“device”% 1142 and %/TEMPLATE% 1144 define a template section for the device object class. The %LOOP% 1146 and %/LOOP% 1148 define a loop section to be repeated for every device found in the directory. The following refers to the first device found in the directory. The %LINK% 1150 and %LINK% 1152 defines a link section for the current device. Based on directory information, the %VAL NAME=“cn”% 1154 is replaced with Directory Publisher. The result of the link section (<A HREF=“cn=DIRECTORY PUBLISHER,ou=SALES, o=XYZCORP,c=US”>Directory Publisher </A>) is displayed by the browser as a link to read Directory Publisher. Based on directory information, the %VAL NAME=“d” DELIMIT=“,”% 1156 is replaced with X 500 Directory, LMS Names Publisher.
The following refers to the second device found in the directory. The %LINK% 1150 and %/LINK% 1152 defines a link section for the current device. Based on directory information, the %VAL NAME=“cn”% 1154 is replaced with LMS. The result of the link section (<A HREF=“cn=LMS,ou=SALES,o=XYZCORP,c=US”>LMS</A>) is displayed by the browser as a link to read LMS. Based on directory information, the %VAL NAME=“d” DELIMIT=“,”% 1156 is replaced with The Lotus Message Switch. The %UPLEVEL% 1158 and %/UPLEVEL% 1160 define an uplevel section. Based on directory information, the result of the uplevel section (<A HREF=“o=XYZCORP,c=US?”>Go UP To Previous Level</A>) is displayed by the browser as a link to list XYZCorp.
To conduct a search, the search template file that is used to create the response and the search form into which the search data is entered are both created. To process the search, the gateway expects a POST from the client with URL to be in the form: “Distinguished name”?“?Search format”.
A Search template file is used to display information for an X.500 entry and all entries below that DN that meet certain criteria. A Search template file is setup in the same format as a List template file. In the case of a Search template file, a template should be defined for each object class that may exist in the sub-tree of the distinguished name.
The following tags may be used in a Search template file: ATTR (X.500 attribute); VAL (X.500 value); DN (current distinguished name); UPLEVEL (hyperlink to List parent DN); LINK (hyperlink to Read current DN); and LOOP (causes the gateway to loop through all the DNs that correspond to the template). All of these tags may be used in the template, while all but LOOP may be used in general text.
FIGS. 12 ( a ) and 12 ( b ) illustrate a search template file and the corresponding search request output. Given the Search template file illustrated in FIG. 12 ( a ), and the submission of search for commonName ending in Doe and objectClass equal to pilotPerson, the response would be that illustrated in FIG. 12 ( b ). Based on directory information, the %DN% 1202 is replaced with ou=SALES,o=XYZCORP,c=US. Based on attribute mappings, the %ATTR NAME=“ou”% 1204 is replaced with Organizational Unit. Based on directory information, the %VAL NAME=“ou”% 1206 is replaced with SALES. The %TEMPLATE OC=“pilotPerson”% 1208 and %/TEMPLATE% 1210 define a template section for the pilotPerson object class. The %LOOP% 1212 and %/LOOP% 1214 define a loop section that will be repeated for every pilotPerson found in the directory.
The following refers to the first pilotPerson found in the directory. The %LINK% 1216 and %/LINK% 1218 defines a link section for the current pilotPerson. Based on directory information, the %VAL NAME=“cn”% 1220 is replaced with John Doe. The result of the link section (<A HREF=“cn=JOHN DOE,ou=SALES,o=XYZCORP, c=US”>John Doe</A>) is displayed by the browser as a link to read John Doe.
The following refers to the second pilotPerson found in the directory. The %LINK% 1216 and %/LINK% 1218 defines a link section for the current pilotPerson. Based on directory information, the %VAL NAME=“cn”% 1220 is replaced with Jane Doe. The result of the link section (<A HREF=“cn=JANE DOE,ou=SALES, o=XYZCORP,c=US”>Jane Doe</A>) is displayed by the browser as a link to read Jane Doe.
The %TEMPLATE OC=“device”% 1222 and %/TEMPLATE% 1224 define a template section for the device object class. Since the search was for cn ending in Doe and objectClass equal to pilotPerson, this template section is ignored.
To create a search form, an administrator: (1) decides on what attributes to search and what distinguished name to use; (2) creates the search format and numbers the parameters; (3) creates the ACTION string; (4) creates the INPUT sections of the form; and (5) creates a template file with template structures for any object classes that may be returned from the search request. In defining a search format, a plurality of search formats are contemplated. For example, the search format may be an LDAP search filter as defined in RFC 1960, with gateway specific modifications. Instead of the values for the attributes, there are placeholders that are used by the gateway to substitute the input data. The gateway receives the search format and the input data at the time the Search request is made. The gateway then creates an actual LDAP search string from the search format and the input data.
The placeholders include the following: $N, which is the value to search for; $T, which is a NOT character (!); $F, which is a filter type for the equality (˜=, >=, <=); and $C, which is a comparison operator (|, &). The filter types are defined as follows: ˜=means “approximately equal to”; >=means “greater than or equal to”; and <=means “less than or equal to”. The comparison operator | (vertical bar) means “or” and & (ampersand) means “and.” The placeholders are used to create the search string format. Each placeholder has an index value associated with it. The index associated with the placeholder is the number associated with the order in which they appear in the string. Indexing the parameters allows the gateway to replace placeholders with actual data.
Once a search format is defined, a form is built. The following HTML tags are used when building a form: (1) METHOD, which is the type of request that is sent when the form is submitted; it preferably is POST; (2) ACTION, which is the URL to be submitted; it preferably is in the form: “Distinguished name”?“?Search format”; and (3) INPUT, which is an input area on the form which follows the form: <INPUT TYPE=type NAME=name VALUE=value>. The TYPE value is preferably one of the following: TEXT, which is an edit box for entering data; RADIO, which is a radio button for selecting one of multiple choices; CHECKBOX, which is a check button for turning an option on or off; SUBMIT, which is a submit button; or RESET, which is a reset button.
In order for the gateway to create the LDAP filter, the form is set up to associate the input areas with the placeholders. This is done by giving the NAME parameter a value containing the index of the placeholder, and having the VALUE value reflect the string that is to be used in the search filter. The NOT operator is a checkbox in the form. Since it is either on or off, only one input line is needed. The VALUE value is an exclamation mark “!”. For example, it may look like: <INPUT TYPE=CHECKBOX NAME=param2 VALUE=“!”>Not.
The COMPARISON operator is a radio button within the form. The form does not need to display these characters, but it is set up to send them to the gateway for processing. The COMPARISON operator is selected by displaying the two possible values. The NAME value for both selections must be the same in order to have the form send only one of the values. The VALUE value for the And operator must be an ampersand and the VALUE for the Or operator must be a vertical bar. One of the radio buttons is automatically selected by using the CHECKED parameter. For example, it may look like: <INPUT TYPE=RADIO CHECKED NAME=param1 VALUE=“&”>And. It may also look like: <INPUT TYPE=RADIO NAME=param1 VALUE=“|”>Or.
The FILTER type operator is a radio button or a checkbox within the form. If more than one choice is given, it preferably is a radio button. If only one choice is given, it preferably is a checkbox. The filter type is used to modify the equality comparison in the filter. It can modify it to be greater than, less than or approximate to.
If more than one choice is given, the NAME value for all selections must be in the same order to have the form send only one of the values, or possibly no value which will leave the equality unaffected. The VALUE value for the greater than operator is the greater than sign (>). The VALUE value for the less than operator is the less than sign (<). The VALUE value for the approximate operator is the tilde (˜). It is not necessary to use the CHECKED parameter because the default is no value. One example of a FILTER type operator is: <INPUT TYPE=RADIO NAME=param3 VALUE=“<”>Less Than.
NAME is a text edit box in the form. If no text is typed into the box, an asterisk (*) is assumed. There are no restrictions on the TEXT input. The user can type wildcards into the text to modify the search criteria. One example is the following: Surname:<INPUT TYPE=TEXT NAME=param4 SIZE=32 MAXLENGTH=2000>.
Preferably all forms have a SUBMIT and RESET button. Selecting the SUBMIT button sends the ACTION value and input data to the gateway. Selecting the RESET button clears all the data entered and sets all buttons to their default values.
FIG. 13 ( a ) illustrates a first example of a search form HTML. This is for a search on the attribute commonName. The LDAP filter may look like: (cn=*Doe), which creates a search on the commonName attribute with a value ending in Doe. The search
format is: (cn$F=$N) 1302 , where $F stands for the equality filter type and $N stands for the value of commonName.
The above search may be modified to only search entries with an object class of pilotPerson. FIG. 13 ( b ) illustrates a second example of a search form HTML. The LDAP filter might look like: (&(cn=*Doe)(objectClass=pilotPerson)). This is a search on the commonName with a value ending in Doe and an objectClass with a value of pilotPerson. The search format is: (&(cn$F=$N)(objectClass=pilotPerson)) 1304 , where $F stands for the equality filter type and $N stands for the value. FIG. 13 ( c ) illustrates a search form output for the examples of FIGS. 13 ( a ) or 13 ( b ).
The above example may be modified to allow the user to look for entries other than pilotPerson, as illustrated by the search form HTML of FIG. 14 ( a ). The search format would be: (&(cn$F=$N)($T(objectClass=pilotPerson))) 1402 , where $F stands for the equality filter type and $N stands for the value of commonName. FIG. 14 ( b ) illustrates a search form output corresponding to FIG. 14 ( a ), and FIG. 14 ( c ) illustrates the corresponding search request output.
A search may also be conducted on the attribute commonName and/or the attribute title, as illustrated by the search form HTML. The LDAP filter may look like: (&(cn=J*)(t˜=Manager)). This is a search on the commonName attribute with a value beginning with J and a title approximately equal to Manager. The search format is: ($C(cn$F=$N)(t$F=$N)) 1502 , where $F stands for the equality filter type, $N stands for the value and $C stands for a compare. FIG. 15 ( b ) illustrates a search form output corresponding to FIG. 15 ( a ), and FIG. 15 ( c ) illustrates the corresponding search request output.
Another embodiment of the invention automatically formats search results into clickable lists, tables, frames and other constructs represented in HTML. For example, once a person is selected from an employee locator, his Internet e-mail address may be selected and automatically placed in the “TO” field of the user's Internet mail client.
In another embodiment of the invention, an administrator can configure various system parameters, including server parameters, LDAP parameters, logging parameters and administrator parameters.
A Server page allows configuration of parameters relevant to the server. These parameters include connection and HTML information. The connection parameters includes Port, Maximum Number of Connections, Maximum Number of Backlog Connections, Idle Disconnect Time-out and Watchdog Timer. Port is the port on which the gateway listens for requests. Maximum connections is the maximum number of requests the gateway processes at one time. This allows the gateway to refuse connections after this maximum has been reached. Maximum backlog connections is the maximum number of requests the gateway will allow pending. Idle disconnect time-out is the number of seconds the gateway allows a request to process before attempting to close the connection. This allows the gateway to limit the amount of time a connection is alive; when this limit is reached, the gateway attempts to close the connection. Watchdog timer is the number of seconds between gateway checks for idle disconnects. This allows the gateway to check all open connections to see if they should be closed. Base path is the path for all requests; all relative URLs are preferably relative to this directory. Default file is the default HTML file. When a request is made, this file is sent.
An LDAP page allows configuration of the LDAP connection parameters. LDAP parameters include host parameters, bind parameters and search time-out parameters. Host parameters include Address and Port. The Address parameter is the IP address of the LDAP server, which allows the gateway to execute LDAP searches on the X.500 directory through the LDAP server. Port is the port of the LDAP server. Bind parameters include User Name and Password. User name is the user (Distinguished Name) the gateway should bind as. Password is the password the gateway should use when binding. Search time-out parameters include Infinite LDAP Time-out and LDAP Search Time-out. The former asks whether it is desired for the LDAP searches to have no time-out. An LDAP search can be configured to have no time-out value. This means that an LDAP search will wait infinitely for results. The latter asks what the LDAP searches time-out value is. An LDAP search can be configured to have a specific time-out value. This means that an LDAP search will wait only this amount of time for results. If this wait time is reached, an error will occur. This parameter is only available if the Infinite LDAP Time-out parameter is not chosen.
A Log page allows configuration of the logging capabilities of the gateway. Logging parameters include Number of Files, Records per File and Log Level. With respect to the number of files, the administrator is asked how many log files should be maintained. Once the maximum number of log records is reached in a log file, the gateway creates a new log file, up to the number of files specified here. Once that number is reached, the oldest log file is overwritten. With respect to Records per File, the administrator is asked what is the maximum number of records per log file. The gateway writes a specified number of log records to a log file before closing that log file and creating a new one. With respect to Log Level, all log messages defined by the gateway are assigned a log level. Only log messages associated with the specified logging level are output to the log. Logging levels include MINIMAL, NORMAL, INTENSIVE and DEBUG. These levels indicate the quality of information the gateway writes to the log files, with MINIMAL being the minimum level and DEBUG being the maximum level.
An Administrator page allows configuration of the Administrator application. The parameter countries is the list of countries that are available for the administrator application. The schema file parameter is the schema file used by the administrator application. This asks the administrator to identify the name and path of the schema file used by the DSA. The schema file is used to obtain object classes and attribute lists.
The administrator also has the ability to customize the appearance of the display of directory information. The administrator may set, inter alia, the background color, the font, the font color, the font size, and the page layout. Further, the administrator may use graphics, such as the organizational logo, on the page. Since directory information is placed into dynamically created HTML documents and displayed in a Web Browser, the administrator may control the page layout. All standard HTML tags may be used in these documents. By writing HTML, the administrator may control the presentation and flow of the document and accordingly the directory information.
Access to the directory information may also be controlled by the administrator. For example, an administrator may desire to allow Web browsers to access employee names, but may not wish for these Web browsers to have access to employee home telephone numbers or addresses. The administrator may choose what information from the directory that is displayed in the Web Browser. The administrator does this by including or excluding the appropriate VAL tags in the document.
In another embodiment, this access list may be based on an organization's hierarchy, providing full directory information access to senior members, and lesser directory information access to lower-ranking members.
Other embodiments and uses of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. The specification should be considered exemplary only, with the true scope and spirit of the invention indicated by the following claims.
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A Web Interface and Method for Accessing Directory Information is disclosed. A Web Interface for Accessing Directory Information comprises a request mapper that links directory data to a template file in response to a directory request, and a friendly name mapper that correlates an abbreviated name to a non-abbreviated name. The abbreviated name refers to at least one entry of said directory data. A method for accessing directory information in accordance with the invention comprises the following steps: (1) receiving a request for directory data; (2) determining whether the request is a distinguished name request, wherein the distinguished name request is a request for a distinguished name; (3) in response to a determination that the request is not a distinguished name request, retrieving a directory resource corresponding to the request; (4) in response to a determination that the request is a distinguished name request, determining whether the distinguished name is mapped; (5) in response to a determination that the distinguished name is not mapped, retrieving an object class of the distinguished name and finding a template using the object class; and (6) in response to a determination that the distinguished name is mapped, finding a template using the distinguished name.
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CROSS-REFERENCE TO RELATED APPLICATION
This application is a divisional of U.S. patent application Ser. No. 09/223,117 filed on Dec. 30, 1998, now U.S. Pat. No. 6,237,672, entitled “SELF LUBRICATING AND CLEANING INJECTION PISTON FOR COLD CHAMBER INJECTION UNIT”, and which is herein incorporated by reference.
FIELD OF THE INVENTION
This invention is in the field of cold chamber die casting machines. More particularly, the invention relates to an injection piston which provides improved injection, lubrication and cleaning of the injection sleeve.
BACKGROUND OF THE INVENTION
The injection piston is comprised of a plunger tip, plunger tip ring, a cap to retain the plunger piston ring on the plunger tip, a lubricating chamber and a scraper and guide ring. The cap, plunger piston ring and scraper and guide ring are fastened to the plunger tip. An annular arcuate recess about the circumference of the plunger tip in combination with a series of tilted and radial lubrication nozzles form a lubrication chamber within the injection sleeve. The extent of the lubrication chamber enables a substantial portion of injection sleeve to be directly lubricated before withdrawal of the plunger tip in the injection sleeve in preparation for the filling cycle.
In cold chamber die casting, the injection piston is located within the injection sleeve of the cold chamber die casting unit. The injection piston is connected by a connecting rod to an injection piston rod to an injection unit piston. The withdrawal of the injection unit piston results in the withdrawal of the injection piston within the injection sleeve to a fill position. In the fill position molten metal is poured into the space in the injection sleeve above the injection piston. Once the dies of the cold chamber die casting machine are closed and clamped, the injection cycle is commenced. In the injection cycle, the injection unit piston drives the piston rod, connection rod and injection piston upwardly within the injection sleeve transporting the molten metal in the injection sleeve into the runners and die cavities. As soon as the molten metal in the dies is firm, the injection unit piston withdraws the injection piston to the fill position within the injection sleeve in position for commencement of the subsequent cycle.
One problem associated with cold chamber die casting machines is that during the injection cycle small amounts of molten metal escape between the inside of the injection sleeve and the injection piston or through a piston ring and form scrap on the interior of the injection sleeve. The problem results from the inside diameter of the injection sleeve expanding and contracting because of thermal expansion caused by receipt of molten metal followed by relative cooling during the injection cycle when the molten metal is removed from the injection sleeve. The injection plunger is also subject to expansion and contraction. Piston rings are also subject to thermal expansion and contraction which may result in a gap through a split ring or rings for the molten metal. It is important that scrap formed from metal be removed from the interior of the injection sleeve to prevent scoring of the injection sleeve which aggravates the problem. Scrap not removed when the injection piston is withdrawn from the interior of the injection sleeve may be removed in the injection cycle and enclosed in a casting resulting in a possible reject.
Another problem associated with cold chamber die casting machines is that the injection piston or the piston ring of the injection piston must be in sliding contact with the surface of the injection sleeve to prevent some molten metal under pressure from escaping between the injection piston and the injection sleeve. The injection piston contacts the injection sleeve during the withdrawal stroke as well as the injection stroke. It is necessary to lubricate the injection piston to prevent wear and lessen scoring by contact movement of the injection piston on the surface of the injection sleeve.
U.S. Pat. No. 5,076,343 discloses a die cast plunger lubrication system. The plunger tip includes a lube groove through which lubrication is forced out on the forward stroke. The disclosure states that the lubricant may be output to the outer surface of the plunger rod instead of through a lube groove. U.S. Pat. No. 4,420,028 discloses an orifice located adjacent to the piston head.
In both the above inventions there is a substantial area of the plunger tip or piston head in contact with the interior of the sleeve. In both patents the lube groove or lube orifice is very small in comparison to the length of the plunger tip.
The plunger tip of the instant invention does not contact the surface of the injection sleeve. The plunger piston ring which is located in an annular recess on the front outside surface of the plunger tip is the first part of the injection piston in permanent contact with the interior of the injection sleeve, the second part is a scraper and guide ring located in an annular recess on the rear side of the plunger tip. The plunger piston ring is retained in the annular recess on the plunger tip by a cap in the form of a disc fastened to the face of the plunger tip. The contact surface between the surface of injection piston and the surface of the injection sleeve is the outer surface of the plunger piston ring. The contact surface of the plunger piston ring is substantially less than that of the contact surface between the plunger or plunger tips disclosed in the above patent. The lubrication chamber and associated annular radial and tilted pressurized air and lubrication nozzles apply pressurized air and lubrication directly to a substantial portion of the injection sleeve initiated upon withdrawal of the injection piston.
Japanese Patent 8,068,257 discloses the use of a series of split rings located side by side on a plunger tip to decrease the surface to surface contact between the injection plunger and injection sleeve. The plunger piston ring of the instant invention does not provide a continuous passage through the ring as does a split ring. The plunger piston ring of this invention is comprised of a ring of tool steel in which a series of parallel alternately disposed inclined slots are cut alternately in the front side and rear side of a ring of tool steel. The inclined slots proceed two-thirds to three-quarters of the distance through the plunger piston ring. The parallel alternate inclined slots result in a plunger piston ring which is flexible without providing any opening extending completely through the plunger piston ring. The plunger piston ring acts as a guide for the plunger tip which is not in contact with the inside of the injection sleeve. The surface area of the plunger piston ring in contact with the surface of the injection sleeve in less than the surface contact of plunger, plunger tips, combined plunger tips and rings or series of plunger split rings used in combination disclosed in the prior art. The lesser surface area contact results in less metal to metal contact between the injection piston and the injection sleeve during each cycle.
SUMMARY OF THE INVENTION
The injection plunger of this invention provides a plunger tip having an annular lubricating chamber commencing behind the plunger piston ring. Forwardly tilted nozzle holes blow pressurized lubricant and air at the interior of the injection sleeve in the vicinity of the plunger piston ring. Radial nozzle holes blow pressurized lubricant and air directly at the surface of the injection sleeve are also located within the annular lubricating chamber. The lubrication and pressurized air blow commences while withdrawal of the injection plunger is initiated and terminates when the injection plunger reaches the fill position. The combined use of tilted and radial nozzles located annularly within the lubricating chamber provides lubrication directly at the surface of the injection sleeve facing the annular lubricating chamber.
Immediately to the rear of the lubricating chamber is a scraper and guide ring whose outer diameter is less than the inside diameter of the injection sleeve. The scraper and guide ring serves to remove metal scores located on the inner wall of the injection sleeve. The rear of the lubricating chamber is vented to the outside by a series of circular openings defining cylindrical conduits through the back of the plunger tip. The series of cylindrical conduits have longitudinal centerlines parallel to the longitudinal centerline of the plunger tip, said apertures being equally spaced about the longitudinal centerline of the plunger tip commencing at the back of the lubricating chamber.
During the injection cycle as the plunger tip moves forward the scraper and guide ring removes scores from the inside of the injection sleeve which fall into the lubrication chamber. Upon initiation of piston withdrawal, lubrication and pressurized air are blown through the tilted and radial nozzles into the lubricating chamber thus driving scrap and loose lubricant out the scrap conduits in the rear of the lubricating chamber.
The injection piston and more particularly the plunger tip, plunger piston ring and cap decrease the amount of molten metal passing by or through the plunger, plunger tip or plunger piston ring resulting in a cleaner surface on the interior of the injection sleeve. The application of lubrication directly to a substantial length of the injection sleeve facing the lubricating chamber commencing proximate the plunger piston ring sleeve decreases the wear on the plunger piston ring and the surface of the injection sleeve. The quality of castings is improved by decreasing solid impurities within the injection sleeve resulting from little molten metal passing between the plunger ring and the injection sleeve combined with improved removal of solids.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of the principle parts of the injection system of a cold chamber die casting machine with the injection piston in retracted position prior to receipt of the molten metal.
FIG. 2 is a cross-sectional view of the injection system of the cold chamber die casting machine of FIG. 1 with the injection piston in the forward position after having forced the molten metal into the runners and die cavities.
FIG. 3 is a partial side and cross-sectional view of the connecting rod, plunger tip, plunger piston ring, and cap with the retaining bolts retaining the cap on the face of the plunger tip and front side of the plunger piston ring.
FIG. 4 is a rear view of the back of the plunger tip of FIG. 3 disclosing a series of scrap exhaust holes.
FIG. 5 is a top view of the plunger piston ring for the plunger tip showing a series of equally special slots commencing in the front side of the plunger piston ring.
FIG. 6 is a side view of the plunger piston ring for application to the plunger tip showing a number of alternately disposed parallel inclined slots in the injection piston ring commencing alternately on the front and rear sides of the plunger piston ring.
FIG. 7 is a top view of the retaining cap for the plunger tip showing a series of equally spaced countersink holes.
FIG. 8 is a cross-sectional view of the retaining cap for the piston ring.
DETAILED DESCRIPTION
Referring to FIG. 1 there is shown a portion of a cold chamber die casting machine 1 and an injection unit 2 for the cold chamber die casting machine. The portion of the cold chamber die casting machine 1 shown in FIG. 1 is the stationary right hand side platen 3 . The stationary die half 4 is mounted on the stationary right hand side platen 3 . FIG. 2 shows the travelling left hand side platen and the travelling die half 5 in closed position in contact with stationary die half 4 . The injection sleeve 6 inclines upwardly within the stationary right hand side platen 3 and ends inside the base of stationary die half 4 . Injection sleeve clamp 7 maintains the injection sleeve 6 in position in the stationary right hand side die half 4 . In FIG. 1 the plunger tip 8 of injection unit 2 is shown near the bottom of injection sleeve 6 in the lower or filling position. The plunger tip 8 is connected by connecting rod 9 to saddle 10 of injection unit 2 . The saddle 10 is in turn connected to injection piston rod 11 which in turn is fastened to the injection unit piston for the injection unit 2 , which piston is not shown. The saddle 10 receives a flexible hose 12 for carrying plunger tip coolant through the saddle 10 . Connector nut 13 is the coolant plug.
As seen in FIG. 3 the plunger tip 8 has an annular recess 14 about the exterior of the front face 15 of the plunger tip 8 . The plunger piston ring 16 is located in the annular recess 14 . The outside diameter of the plunger piston ring 16 is greater than the outside diameter of the plunger tip 8 and in fixed and moving contact with the inside of the injection sleeve 6 . The injection piston ring 16 is maintained in the annular recess 14 by the cap 17 which is secured to the face 15 of the plunger tip 8 by threaded retaining bolts 18 which are placed in openings defining apertures 19 in cap 17 and secured in openings defining threaded apertures 20 located on the face 15 of the plunger tip 8 .
Referring to FIG. 3 the side of the plunger tip 8 includes an annular recess 14 commencing behind the plunger piston ring 16 and extending for over a third of the length of the plunger tip 8 . When the plunger tip 8 is placed in the injection sleeve 6 as seen in FIG. 3, the annular groove creates a lubrication chamber 24 . A series of radial lubrication and air nozzles 25 are located annularly about the longitudinal centerline of the plunger tip 8 . A series of forwardly inclined lubrication and air nozzles 26 are also located annularly facing towards the front of the plunger tip 8 . The radial lubrication and air nozzles 25 and the inclined lubrication and air nozzles 26 are connected through lubrication and air conduits 27 and 28 to the same annular lubrication and air supply conduit 29 located on a front surface of the connecting rod 9 . The annular lubrication and air supply conduit 29 is connected through the connecting rod lubrication and supply conduit 30 to the pressurized lubricant and air supply in the saddle 10 which in turn is supplied through the flexible hose for pressurized lubricant and air supply 31 .
An annular scraper and guide ring recess 32 located near the rear or the plunger tip 8 immediately behind the lubrication and air chamber 24 has a scraper and guide ring 33 mounted therein. The outside diameter of the scraper and guide ring 33 is slightly less than the inner diameter of the injection sleeve 6 . The scraper and guide ring is split in half by an inclined slot. The scraper and guide ring is mounted on the plunger tip 8 in an annular recess on the plunger tip. The inclined slot provides flexibility to the scraper and guide ring. A series of cylindrical openings defining scrap exhaust cylinders 34 extend from the back of the lubrication chamber 24 through the rear wall 35 of the plunger tip 8 . As seen in FIGS. 3 and 4, the centerlines of the scrap exhaust cylinders 34 are parallel to the longitudinal centerline of the plunger tip 8 . FIGS. 3 and 4 also disclose a central opening in the plunger tip 8 defining a cylindrical space 36 within the plunger tip 8 . A cylindrical conduit 37 extending through the connecting rod 9 is used to circulate a coolant to control the temperature of the plunger tip 8 .
Referring to FIG. 5, there is disclosed a plunger piston ring 16 having a series of inclined parallel slots 21 with alternate slots 21 commencing from the front 22 and rear 23 sides of the plunger piston ring 16 . The slots 21 are inclined at 15° relative to a plane on the longitudinal centerline of the plunger piston ring 16 . The slots 21 extend from the front 22 or rear 23 of the plunger piston ring 16 . The slots 21 extend from the front 22 or rear 23 of the plunger piston ring 16 two-thirds to three-quarters of the distance towards the opposite side of the plunger piston ring 16 . The multiple slots 21 , forty-eight in number, are twenty thousands of an inch wide. The multiple parallel inclined alternate slots provide flexibility but no passage from the front side through to the rear side of the plunger piston ring. The plunger piston rings 16 , are machined from tool steel. After cutting the slots 21 in the injection piston ring 16 the injection piston ring 16 is metal hardened, finished and subsequently nitrided.
The cap 17 shown in FIGS. 7 and 8 is also machined from tool steel so that the cap 17 and injection piston ring 16 which are in contact with one another have the same coefficient of thermal conductivity. The plunger piston ring 16 is mounted sliding fit into the injection sleeve 6 .
The plunger tip 8 machined from high strength beryllium copper mold alloy has a higher coefficient of thermal conductivity than tool steel. The cap 17 and plunger piston ring 16 made of tool steel have a lower coefficient of thermal conductivity than the alloy of the plunger tip to keep the molten metal in the injection sleeve liquid during filling and injection. The high strength beryllium copper alloy of the plunger tip 8 has a high coefficient of thermal conductivity which enables the tip 8 to be cooled by water circulating through the central base of the plunger tip 8 . The high strength beryllium copper alloy of the plunger tip 8 provides peak hardness and superior wear resistance compared to that of tool steels.
The alternate opposed inclined parallel slots 21 in the plunger piston ring provide the plunger piston ring 16 with flexibility so that if the injection sleeve 6 becomes uneven due to thermal expansion the outside of the plunger piston ring 16 remains in contact with the inside wall of the injection sleeve 6 . The flexibility of the injection piston ring 16 provides less wear on the inside of the injection sleeve 6 than conventional thermal tips without plunger piston rings or split rings which permit some molten metal to bypass the split rings when they are subject to thermal expansion and pressure. The position of the injection piston ring 16 at the front outside corner of the plunger tip 8 provide a guiding advantage for the plunger tip 8 . When the injection piston ring 16 and the injection sleeve 6 wear, the invention provides for easy removal of the plunger piston ring 16 and substitution of the same or a slightly larger plunger piston ring 16 . The worn plunger piston ring is removed by removal of the threaded retaining bolts 18 , removal of cap 17 , removal of piston ring 16 and substitution of a new plunger piston ring 16 , which may be the same size or slightly larger depending on sleeve wear and condition, which is then secured to the plunger tip 8 as earlier described.
In operation, the cycle commences with the injection unit 2 in the fill position shown in FIG. 1 . As seen in FIG. 2 the travelling left hand side platen and travelling die half 5 are open and a sufficient distance from the stationary right hand side platen 3 and stationary die half 4 to permit molten metal to be poured into the injection sleeve 6 . Molten metal is poured into the open injection sleeve 6 . The molten metal in the injection sleeve 6 is in contact with the sides of the injection sleeve 6 , cap 17 , and the edge of the plunger piston ring 16 . The cap 17 and the plunger piston ring 16 are machined from tool steel which has a low coefficient of thermal conductivity relative to the plunger tip 8 . The low coefficient of thermal conductivity of the cap 17 and the plunger piston ring 16 assist in maintaining the molten metal in contact with the cap 17 and plunger piston ring 16 in a fluid state.
When the pouring of the molten metal into the injection sleeve 6 is complete, the travelling left hand side platen and travelling die half 5 close on stationary right hand side platen 3 and stationary die half 4 . Following closing the die halves are clamped shut and the injection unit 2 moves from the open position shown in FIG. 1 to the injection position shown in FIG. 2 . As the injection unit 2 moves upwardly in injection sleeve 6 the scraper and guide ring 33 of injection plunger 8 scrapes any metal scores located on the inside of the injection sleeve 6 into the lubrication chamber 24 .
As the injection unit 2 moves from the fill position shown in FIG. 1 to the injection position shown in FIG. 2 the molten metal is forced from injection sleeve 6 into die halves 4 and 5 . When the molten metal has solidified the clamping pressure is released and lubrication mixed with air is blown onto the surface of the injection sleeve 6 through inclined lubrication and air nozzle 26 and radial lubrication and air nozzles 25 . The inclined lubrication and air nozzles 26 are directed at the injection sleeve 6 immediately behind the plunger piston ring 16 . As the inclined lubrication and air nozzles 26 and radial lubrication and air nozzles 25 are located around the circumference of the generally arcuate annular recess in plunger tip 8 , all the surface of the injection sleeve 6 facing the lubrication chamber 24 is lubricated. Following termination of clamping pressure and commencement of lubrication the injection unit 2 is withdrawn from the injection position shown in FIG. 2 to the fill position shown in FIG. 1 . When the injection unit 2 reaches the fill position, the lubrication is turned off and the injection unit 2 is ready for commencement of the next sequence.
Following release of clamping pressure after the molten metal has solidified the moving platen and travelling die half 5 are withdrawn from the fixed platen 3 and fixed die half 4 .
The injection piston comprised of the plunger tip 8 , the flexible plunger piston ring 16 and cap 17 are effective in preventing molten metal from bypassing plunger piston ring 16 through which molten metal under pressure may escape.
The plunger piston ring 16 does not provide any path through the plunger piston ring 16 . The location of inclined lubrication and air nozzles 26 and radial lubrication and air nozzles 25 about the circumference of the generally arcuate annular recess in the plunger tip 8 provides for lubrication of all the inner surface of the injection sleeve 6 facing the lubrication chamber 24 . The scraping and removal of debris through exhaust conduits 34 during the injection stroke decreases wear of the surface injection sleeve 6 and the plunger piston ring 16 .
The invention in its broadest aspect relates to a plunger tip 8 having a lubrication chamber 24 with inclined lubrication and air nozzle 26 and radial lubrication and air nozzles 25 about the generally arcuate annular recess in the plunger tip 8 . While the invention in its broadest aspect has been described in association with a plunger tip 8 having a plunger piston ring 16 and a cap 17 , it will be recognized by those skilled in the art that the lubrication chamber 24 together with inclined lubrication and air nozzles 26 and radial lubrication and air nozzles 25 about the generally arcuate annular recess in the plunger tip 8 may be utilized as part of plunger tips utilizing other means to prevent molten aluminum to pass between the plunger tip 8 and the injection sleeve 6 .
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A method for cleaning and lubricating an injection sleeve and plunger tip during a fill and injection cycle in a cold chamber die casting machine, in which the plunger tip has an annular generally arcuate recess, lubricating nozzles, lubricating conduits, and scrap exhaust conduits. Pressurized air is released into the recess during the injection cycle and debris is exhausted through the scrap exhaust conduits. Upon completion of the injection cycle, the release of pressurized air into the recess is terminated. A mixture of pressurized air and lubricant is released through the recess onto the injection sleeve during the withdrawal cycle. Upon completion of the withdrawal cycle, release of the mixture of pressurized air and lubricant into the recess is terminated.
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CROSS REFERENCE TO A RELATED APPLICATION
This application is a division of patent application Ser. No. 08/916,106, filed Aug. 21, 1997.
BACKGROUND OF THE INVENTION
The invention relates to an arrangement and a method for determining the penetration depth when putting in place supporting elements into a water bed.
When placing piles or beams into a water bed, information on their loading capacity is often required. Generally for this, markings at fixed distances are placed on the beam elements to be put in place and the number of pile drives which must be made by a pile device are counted in order to achieve a certain penetration depth of the beam element. The number of pile drives gives an indication of the ground conditions and loading capacity, when taking account of the energy consumed. The known method is suitable for the putting in place of beam elements through water or on land, as well as foundation work in which the beam element and the pile device are located underwater.
In the case of underwater pile-driving, which may take place in depths of more than 1000 m, with a known arrangement for determining the penetration depth, an underwater camera is employed which permits an optical control of the markings on the supporting elements. The known arrangement on the one hand has the disadvantage that underwater cameras are prone to failure and with a breakdown, lead to the costly halting of the pile-driving operation. A further disadvantage lies in the fact that for monitoring the putting in place of the beam elements, a person is required to observe a monitor, and to manually protocol the progress of penetration.
SUMMARY OF THE INVENTION
It is the object of the invention to provide an arrangement and a method for determining the penetration depth when putting in place supporting elements into a water bed, which concerns simple principles, is less prone to breakdowns and which can be automised.
This object is achieved with a arrangement according to the invention which is characterised by a pressure sensor for measuring the water pressure and which is fastenable to the supporting element or to a device connected to the supporting element, by a device for transmitting the readings supplied by the pressure sensor and by an evaluation unit for determining the reading differences which arise during the sinking of the pressure sensor on penetration of the supporting element into the water bed.
The object with regard to the method is achieved by way of the following method steps, whilst using a pressure sensor suitable for measuring water pressure and fastened underwater to a supporting element or to a device connected to the supporting element:
before the beginning or during the putting in place of a supporting element, a first reading of the pressure sensor is taken and is kept as a reference value;
after consuming a certain amount of energy for the putting in place of the supporting element or after the completion of the time interval required for this, a further reading of the pressure sensor is taken and retained,
from the difference of the preceding and further readings, the penetration depth achieved by the intermediate putting in place is calculated, preferably by multiplication of the difference by a suitable calibration factor;
in the case that the desired penetration depth is not yet sufficient, the method steps from the second method step are repeated.
The arrangement according to the invention and the method according to the invention have the advantage that instead of a complicated constructed, highly sensitive and accident prone underwater camera, essentially only the pressure sensor at the location of the foundation work must be accomodated underwater at a great depth. A further advantage lies in only having to fasten the pressure sensor to the supporting element or to the device connected to the supporting element, without requiring an exact adjustment as is the case with an underwater camera. Principally, the invention lies in the fact that the pressure sensor is likewise sunk corresponding to the sinking of the supporting element into the water bed, and that from the difference in water pressure in the sunk and in the non-sunk condition, a difference in height is computed.
With this it is neither necessary for the pressure sensor to be sunk with the supporting element into the water bed nor for it to be rigidly fastened to the supporting element. On the contrary, the pressure sensor may be attached at a considerable height above the supporting element, for example on the device putting in place the supporting element into the water floor. It would also be possible to fasten the pressure sensor onto a lever which on the one hand is in connection with the device and on the other hand with a fixed point, and which transmits the sinking movement of the supporting element for example into a greater sinking of the pressure sensor.
An evaluation unit, for determining the reading differences which occur as a result of the sinking of the pressure sensor on penetration of the supporting element into the water bed, is preferably accomodated above water, for example on a ship, but it may also be accomodated underwater for example directly on the pressure sensor or a diving station located underwater for observation.
From the pressure sensor the readings reach the evaluation unit via a transmission device. With this, the transmission of readings may be effected without wire, for example by way of sound signals.
In a preferred embodiment form of the arrangement according to the invention it is however provided that the pressure sensor supplies electrical signals as readings and that these signals or signals gained by convertion are transmitted to the evaluation the occasional control by an observer is made possible.
In order to permit the use of the arrangement according to the invention in water depths of up to 2000 m which might occur, and to simultaneously ensure a measurement of the penetration depth to an accuracy of 1 cm, it is recommended that the pressure sensor is suitable for measuring absolute pressure in the order of 200 bar and has a measuring accuracy in the order of 1 mbar.
In a preferred embodiment form of the arrangement according to the invention, the signal of the pressure sensor consists of an analog electrical quantity, preferably a current which is converted via an analog to digital converter into a digital signal and is transmitted to the evaluation unit. This embodiment form is particularly recommended when the pressure sensor is located at a great water depth, for example 2000 m deep, and the evaluation unit is located on the water surface. In this case, due to the large transmission path, only a digital transmission can be considered for the transmission of the readings with the highest accuracy.
A water depth of 2000 m requires a pressure sensor which can measure absolute pressures of up to 200 bar with a resolution of 1 to 2 mbar. For transmitting such a large range of measurement with the required measuring accuracy, an analog to digital converter with a digital definition of at least 18 bits would be necessary. Such analog to digital converters are complicated and expensive.
Alternatively one may consider pressure sensors which comprise an output with a frequency which is dependent on pressure or a digital serial output, thus permitting the definition required.
Commercially available and inexpensive analog to digital converters however only have a digital resolution of 12 bits. If the measuring range for the water depth is to reach from 0 to 2000 m, with a signal transmission with 12 bits a measuring accuracy of only 0.5 m to 1 m is possible, although the analog signal of the sensor offers a considerably higher accuracy.
For solving this problem, in a further development of the invention it is provided that between the pressure sensor and the analog to digital converter there is connected an electronic subtractor and an amplifier, by which means a preselectable part measuring range may be expanded over the whole conversion range of the analog to digital converter. By way of this, the complete resolution of the analog to digital converter is available for a smaller analog part range. If for example the analog part measuring range is reduced from 2000 m to approximately 80 m, with a 12 bit analog to digital converter a resolution of 2 cm may be achieved.
A further alternative is presented by the use of pressure sensors with integrated logic for a highly accurate reading acquisition and digital data transmission interface.
If the pressure sensor is fastened to pile hammer serving to pile-drive piles into the water floor and the supply lines of the pile hammer also comprises the signal lead of the pressure sensor, it is useful that a computer provided for the monitoring and control of the pile hammer also serves the acquisition, storage and evaluation of the readings of the pressure sensor. A special computer for determining the penetration depth is not then necessary. Preferably this computer also registers the number of pile drives and computes the energy sum used for this.
With the simplist embodiment form of the method according to the invention, the penetration depth is determined from the difference of the preceding reading and the further reading in that the difference is multiplied by a suitable calibration factor. In this way one generally obtains a sufficient measuring accuracy, since under ideal conditions the calibration factor in the first approximation is the same multitude for all readings. Real pressure sensors however do not display a linear behaviour, particularly at the limits of their measuring ranges. For increasing the measuring accuracy therefore, depending on the absolute size of the reading, differing calibration factors may be employed. Particularly when using a computer for computing the differential penetration depth, this action may be carried out without a significant additional effort.
For improving the linearity and accuracy of the conversion function of pressure into depth, preferably a tidal compensation and a gravitational acceleration compensation dependent on location is carried out, as well as taking into account a depth dependent density change function of the water.
In a further development of the method according to the invention it is provided that during the measuring interval, further data is extracted and retained from the device for putting in place the supporting element, particularly data for determining the required amount of energy for putting in place the supporting element. By way of this measure, the method is improved in that not only is the simple determination of the penetration depth per se possible, but also an estimation of the resistance of the water floor to the putting in place of the supporting element into the reached penetration depth.
In a further development of the method it is provided that for each retained reading, a point in time is also registered. With this, with a later evaluation of the readings the chronological progress of the putting in place may also be represented.
The method may be further improved in that the penetration depths calculated from the readings are represented on a diagram. With this the penetration depths may be selectively plotted against time intervals, against the energy required for putting in place (number of pile drives) or also against the energy used with regard to a fixed difference in penetration depth. The representation on a diagram has the advantage that with one look one can acquire the history, progress and the status of the placing procedure, and any erroneous readings as a result of disturbances become immediately visible.
In a further development of the method, it is provided that before the beginning of the determination of the penetration depth the reading of the pressure sensor is reduced to almost zero by way of an electronic subtractor and the residual value is amplified by a preadjustable multiplication factor by way of an amplifier, wherein the size of the multiplication factor is preselected such that the amplified residual value, with the maximum expected penetration depth, does not exceed the highest analog value which can be processed by a subsequently connected analog to digital converter. The advantages of this measure lie in the improved measuring accuracy with a given limited digital resolution of the analog to digital converter. By way of the mentioned adaptation of the multiplication factor, the part measuring range employed is optimally taken advantage of.
The method can be improved even further in that the reduction of the reading of the pressure sensor by way of the subtractor is automatically effected before the beginning of the determination of the penetration depth. This measure simplifies the application of the method and avoids losing time by way of erroneous operation.
The invention may also already be realised by the use of pressure sensor, known per se and suitable for measuring water pressure, for determining the penetration depth from the pressure differences arising when putting in place supporting elements into a water bed. At the same time it is useful to apply the method described earlier.
BRIEF DESCRIPTION OF THE DRAWINGS
One embodiment example of the invention is hereinafter described in more detail by way of the drawings. The figures show individually:
FIG. 1 a pile device on the sea bed with an arrangement according to the invention for determining the penetration depth;
FIG. 2 a sensor unit with a pressure sensor, subtractor, amplifier and analog to digital converter;
FIG. 3 a sensor unit with a pressure sensor and a high resolution analog to digital converter;
FIG. 4 a sensor unit with a pressure sensor and frequency exit; and
FIG. 5 a sensor unit with a pressure sensor and a digital serial interface.
DESCRIPTION OF PREFERRED EMBODIMENTS
In FIG. 1 there is shown a pile device with a pile hammer 1, a pile 2 and a bundle of supply lines 3. The pile hammer 1 is arranged sitting on the pile 2 underwater. The pile device is located at a large depth below the surface of the sea 4 and directly above the sea bed 5 into which the pile 2 is to be put in place. For pile-driving the pile 2, the pile hammer 1 exerts onto this a series of pile drives, wherein the pile hammer 1 together with the pile 2 sink in the direction of the arrow 6.
At the upper end of the pile hammer 1 there is fastened a pressure sensor 7 for measuring the water pressure. The pressure sensor 7 measures the water pressure corresponding to its actual depth 8 under the sea surface 4.
On sinking the pile 2 into the sea bed 5 the pressure sensor also together with the pile hammer 1 sinks, wherein the measured water pressure increases. At the begining of the pile-driving the pressure sensor 7 is located at an initial depth 9 below the sea surface 4 at which a small water pressure is measured. The difference in depth between the initial depth 9 and the actual depth 8 corresponds to a difference in pressure which is evaluated by subtraction of the measured water pressure at the initial depth 9 and at the actual depth 8 in each case.
The pressure sensor according to FIG. 2 supplies an electrical current 11 which is proportional to the pressure and which is converted into a digital signal by way of an analog to digital converter 12 and transmitted to an evaluation unit 16. Between the pressure sensor 7 and the analog to digital converter 12, an electronic subtractor 13 and an amplifier 14 are connected, these serving to expand a preselectable part measuring range of the pressure sensor 7 over the whole conversion range of the analog to digital converter 12. This procedure is described in more detail further below.
The current 11 supplied from the pressure sensor 7 is digitalized by the analog to digital converter 12 and is transmitted to an evaluation unit 16 located on an operating ship which is not shown, via an electrical signal lead 15 which is contained in the bundle of supply lines. The evaluation unit 16 comprises a computer which is not shown but which automatically acquires, stores and from the reading differences, constantly computes and displays the difference in depth 10 corresponding to the penetration depth of the pile 2.
Since such pile-driving is carried out in depths of up to 200 m below the surface of the sea 4, the pressure sensor 7 is suitable for measuring absolute pressures of up to 200 bar. On the other hand it has a measuring accuracy of 1 mbar so that the difference in depth 10 which corresponds to the penetration depth of the pile 2 may be calculated to within 1 to 2 cm.
The determination of the penetration depth of the pile 2 is effected in detail by way of the method described hereinafter.
Before the beginning of the pile-driving of the pile 2 the pressure sensor 7 is located at the initial depth 9. In this situation from the computer of the evaluation unit 16, a first reading of the pressure sensor 7 is taken and is stored as a reference value. The computer also controls and monitors the pile driver 1 and in particular registers the number of pile drives carried out from which, taking account of further technical details of the pile device, one can calculate the energy consumed for pile-driving the pile 2. After consuming a certain quantity of energy, i.e. after carrying out a certain number of pile drives, the computer registers a further reading of the pressure sensor 7 and also stores this. Following this, from the difference of the preceding and subsequent reading, by way of multiplication of this difference by a predetermined calibration factor, the computer calculates the penetration depth 10 between these readings. When the desired penetration depth is reached then the method can then here be stopped.
Generally one however desires a protocol of the pile-driving procedure in the form of a diagram with a larger number of readings which for example are plotted against time or against the number of pile drives or against the penetration depth. In these cases the method steps are repeated from the second step, i.e. after the expiry of a predetermined number of pile drives a further reading is taken, stored and from the difference from the preceding reading, a further differential penetration depth is calculated which is in turn represented on the diagram. Of course the computer may also calculate the total penetration depth achieved since the first reference value.
Since the analog to digital converter 12 used in FIG. 2 only has a digital resolution of 12 bits, the analog current 11 supplied from the pressure sensor 11 may not be processed over the whole measuring range of 200 bar with the required resolution of 1 to 2 mbar. In order however to maintain a sufficient resolution over the whole measuring range, the subtractor 13 and the amplifier 14 are connected between the pressure sensor 7 and the analog to digital converter 12.
This arrangement is represented schematically in FIG. 2. By way of a voltage 20 which is constant during the determination of the penetration depth 10, the analog voltage 11 supplied by the pressure sensor 7 is reduced to almost zero before the beginning of the above mentioned method. This may be effected without further ado in that the resetting procedure is triggered by a start signal sent from the evaluation unit 16. At the same time a suitable electronic circuit may determine and after resetting, maintain the required constant voltage 20 by measurement of the momentary voltage supplied by the pressure sensor 7.
The residual value 17 remaining at the output of the subtractor 13, as has been stated, is firstly set to almost zero, but slightly increases during the course of the pile-driving of the pile 2. In order to be able to better exploit the digital resolution of the analog to digital converter 12, the remaining residual value 17 must be amplified. This is effected in the subsequently connected amplifier 14 which effects a multiplication of the residual value 17 by an amplification factor 18. At the output of the amplifier 14 resides the amplified residual value 19 which is transmitted to the input of the analog to digital converter 12. The amplification factor 18 is preselected such that the amplified residual value 19, at the maximum expected penetration depth 10, does not exceed the analog value which can be processed by the subsequently connected analog to digital converter 12.
Due to a such an attained expansion of the part measuring range of the pressure sensor 7, despite the limited digital resolution of the analog to digital converter 12, the expanded part range is transmitted via the signal lead 15 to the evaluation unit 16 with a sufficient measuring accuracy.
With a modification of the invention represented in FIG. 3, the subtractor and amplifier are redundant since here a high resolution analog to digital converter 21 is employed which comprises a resolution of more than 12 bits.
With a further modification of the invention shown in FIG. 4, the pressure sensor 7 produces two frequency signals 23 and 24 which are digitalized in two frequency-digital transducers 25 and 26. With this, a first frequency signal 23 is dependent on the water pressure at the location of the pressure sensor 7 whilst the second frequency signal 24 is dependent on the temperature at the location of the pressure measurement and is provided for compensating temperature dependent deviations of the pressure reading.
In the evaluation unit which is not shown, the digital signals are evaluated from the frequency-digital transducers 25, 26 and the pressure at the location of the pressure sensor 7 is computed to a high accuracy. With this computation, apart from the two frequency signals 23, 24 of the pressure sensor 7, also further coefficients for correcting the reading are taken into account.
With the further modification of the invention shown in FIG. 5, the sensor unit is equipped with a digital serial interface 22 which is connected to the output of the pressure sensor 7 whose signal it digitalizes and serially transmits to the evaluation unit 16.
LIST OF REFERENCE NUMERALS
1 pile hammer
2 pile
3 supply lines
4 surface of the sea
5 sea bed
6 direction
7 pressure sensor
8 actual depth
9 initial depth
10 difference of depth/penetration depth
11 current
12 analog to digital converter
13 subtractor
14 amplifier
15 signal lead
16 evaluation unit
17 residual value
18 amplification factor
19 amplified residual value
20 constant voltage
21 analog to digital converter
22 digital serial interface
23 first frequency signal
24 second frequency signal
25 first frequency-digital transducer
26 second frequency-digital transducer
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In a method for determining depth when putting in place supporting elements into a waterbed, a pressure sensor fastenable to a supporting element or a device connected to the supporting element measures a water pressure, the reading is supplied by the pressure sensor and transmitted via signal lead to an evaluating unit which determines the penetration depth of the supporting element from the reading differences which occur during the sinking of the pressure sensor on penetration of the supporting element into the waterbed.
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CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 10/814,109, filed on Mar. 30, 2004, now U.S. Pat. No. 7,425,540, the contents of which is herein incorporated by reference.
FIELD OF THE INVENTION
The instant invention relates generally to protein-protein interactions that regulate intra and intercellular communication; particularly to methods for modification of protein-protein interactions; and most particularly to a method for ameliorating pain in a subject by modifying the activity of NMDA (N-methyl-D-aspartate) receptors located in cells by inhibition of the interaction of the unique domain of the tyrosine kinase Src enzyme with proteins of the NMDAR complex.
BACKGROUND OF THE INVENTION
Excitatory transmission at central synapses is primarily mediated by the amino acid glutamate acting through postsynaptic ionotropic receptors (Dingledine et al. Pharmacological Review 51:7-61 1999). The N-methyl-D-aspartate receptor (NMDAR) is one such type of ionotropic glutamate receptor (Dingledine et al. Pharmacological Review 51:7-61 1999). NMDARs are multiprotein complexes located at excitatory synapses within the postsynaptic density (PSD) comprised of the core channel subunits together with associated scaffolding and regulatory proteins that control receptor localization, ionic flux through the receptor and downstream signaling events (Scannevin et al. Nature Reviews Neuroscience 1:133-141 2000; Sheng et al. Annual Review of Physiology 62:755-778 2000). NMDAR's are crucial for central nervous system (CNS) development, neuroplasticity and pathophysiology (Dingledine et al. Pharmacological Review 51:7-61 1999; Sheng et al. Science 298:776-780 2002). Multiple factors regulate NMDAR function, including dynamic cycling of protein phosphorylation and dephosphorylation at serine/theronine or tyrosine residues (Wang et al. Nature 369:233-235 1994; Smart Current Opinion in Neurobiology 7:358-367 1997). The Src protein is one such factor that modulates the activity of the NMDARs (Yu et al. Science 275:674-678 1997; Lu et al. Science 279:1363-1368 1998; Yu et al. Nature 396:469-474 1998).
The non-receptor protein tyrosine kinase Src is a ubiquitous enzyme with key roles in diverse development, physiological and pathological processes (Brown et al. Biochim. Biophys. Acta 1287:121-149 1996). Domains identified in Src- the Src homology 3 (SH3) domain, the SH2 domain and the SH1 (catalytic) domain are signature regions that have been used to define highly-conserved protein modules found in a wide variety of signaling proteins (Pawson Nature 373:573-580 1995). In addition to these highly-conserved regions, Src also contains a region of low sequence conservation and unknown function, termed the unique domain.
Src is highly expressed in the CNS, functioning to regulate glutamatergic neurotransmission and synaptic plasticity (Ali et al. Current Opinion in Neurobiology 11:336-342 2001; Salter and Kalia Nature Reviews:Neuroscience 5:317-328 2004)). At glutamatergic synapses, Src modulates the activity of NMDARs (Yu et al. Science 275:674-678 1997; Lu et al. Science 279:1363-1368 1998; Yu et al. Nature 396:469-474 1998). Src represents a point through which multiple signaling cascades from G-protein coupled receptors (Luttrell et al. Journal of Cell Science 115:455-465 2002), Eph receptors (Henderson et al. Neuron 32:1041-1056 2001; Takasu et al. Science 295:491-495 2002; Murai et al. Neuron 33:159-162 2002) and integrins (Lin et al. Journal of Neurophysiology 89:2874-2878 2003; Kramar et al. Journal of Biological Chemistry 278:10722-10730 2003) converge to upregulate NMDAR channel activity, thus mediating essential neuronal excitation. The upregulation of NMDAR activity by Src is necessary for long-term potentiation (LTP) of synaptic transmission at Schaffer collateral-CA1 neuron synapses in the hippocampus (Ali et al. Current Opinion in Neurobiology 11:336-342 2001), the predominant cellular model for learning and memory (Kandel Science 294:1030-1038 2001).
However, abnormal regulation of NMDARs can have numerous pathologic effects; most resulting from the production of nitric oxide, a signaling molecule which mediates excitotoxicity (Dawson et al. Proceedings of the National Academy of Science USA 88:6368 1991). NMDARS mediate ischemic brain injury, as seen, for example in stroke and traumatic injury (Simon et al. Science 226:850 1984). In addition, abnormal NMDAR regulation has been implicated in Alzheimer's disease, Parkinson's disease (Coyle et al. Science 262:689 1993), schizophrenia (Hirsch et al. Pharmacology Biochemistry and Behavior 56(4):797-802 1997), epilepsy (U.S. Pat. No. 5,914,403), glaucoma (US Application. 2002 0077322 A1) and chronic pain (Guo et al. Journal of Neuroscience 22:6208-6217 2002).
Although NMDARs are implicated in numerous pathological conditions, non-selective blocking of their function is deleterious, since complete blockade of synaptic transmission mediated by NMDA receptors is known to hinder neuronal survival (Ikonomidou et al. Lancet: Neurology 1:383-386 2002; Fix et al. Experimental Neurology 123:204 1993; Davis et al. Stroke 31:347 2000; Morris et al. Journal of Neurosurgery 91:737 1999).
Additionally, inhibition of Src kinases may also have deleterious results. Since kinases play a part in the regulation of cellular proliferation, they are frequently targeted for the development of new cancer therapies.
The majority of these therapies inhibit function of the kinase catalytic domain, which is often highly conserved between distinct kinases. Thus, inhibition of Src in the CNS with a standard kinase inhibitor may cross-react with additional kinases and adversely affect normal neuronal functions.
Considering the above-mentioned deleterious effects resulting from direct blockage of NMDARs and/or indirect inhibition of NMDARs through the use of kinase inhibitors, it is clear that there remains a need in the art for a method of modifying NMDARs which can attenuate downstream NMDAR signaling, without completely blocking, ion-channel activity.
DESCRIPTION OF THE PRIOR ART
Since the NMDA receptor is critical to both normal neuronal function and pathology, there are many known methods for modification of NMDA receptors; several examples of which are noted below.
U.S. Pat. No. 5,888,996 (David Farb) discloses a method for inhibiting NMDA glutamate receptor-mediated ion channel activity by treatment with an effective amount of a derivative of pregnenolone sulfate. This patent also discloses a method for modulating/altering excitatory glutamate-mediated synaptic activity by contacting neurons with pregnenolone sulfate or a derivative of pregnenolone sulfate.
U.S. Pat. No. 5,914,403 (Nichols et al.) discloses agents capable of modifying neuroexcitation through excitatory amino acid antagonists; in particular quinolinic acid derivatives antagonistic to a glycine binding site in the NMDAR complex. The agents disclosed by Nichols et al. have anticonvulsant activity.
U.S. Pat. No. 4,994,446 (Sokolovsky et al.) discloses a drug system comprising a MK-801/PCP type drug administered in combination with/or in sequence with excitatory amino acids such as, glutamate, glycine, aspartate and analogs thereof. The excitatory amino acids facilitate binding of the drug to the NMDAR channels. This drug system has anticonvulsant activity and can alleviate brain damage due to stroke.
U.S. Pat. No. 6,653,354 (Franks et al.) discloses a method for reducing the level of NMDAR activation by use of the NMDA antagonist, xenon to inhibit synaptic plasticity. The xenon composition of Franks et al. also acts as a neuroprotectant.
US Patent Application 2002 0123510 A1 (Chenard et al.) discloses a method for treatment of traumatic brain injury (TBI) and stroke by administration of a NR2B subtype selective NMDAR antagonist in combination with either of the following agents; sodium channel antagonist, nitric oxide synthase inhibitor, glycine site antagonist, potassium channel opener, AMPA/kainate receptor antagonist, calcium channel antagonist, GABA-A receptor modulator, anti-inflammatory agent or a thrombolytic agent. These agents either protect neurons from toxic insult, inhibit inflammatory responses after brain damage or promote cerebral reperfusion after hypoxia or ischemia.
Planells-Cases et al. (Mini Review of Medicinal Chemistry 3(7):749-756 2003) disclose that small molecule antagonists of the NMDAR are useful for the treatment of neuropathic pain caused by injury to the peripheral or central nervous system.
US Patent Application 2002 0077322 A1 (George Ayoub) discloses methods for protecting neuronal cells from glutamate-induced toxicity, such as that which occurs in ischemia and glaucoma, by increasing the activity of a cannabinoid agonist which binds specifically to a cannabinoid receptor.
US Patent Application 2003 0050243 A1 (Michael Tymianski) discloses a method for inhibition of binding between NMDARs and neuronal proteins. The inhibition is created by administration of a peptide replacement of either an NMDAR or neuronal protein interaction domain. Post-synaptic density protein 95 (PSD-95) couples NMDARs to pathways mediating excitotoxicity and ischemic brain damage. The method of Tymianski involves transducing neurons with peptides that bind modular domains on either side of the NMDAR/PSD-95 interaction complex. This transduction attenuates downstream NMDAR signaling without blocking receptor activity, protects cortical neurons from ischemic insult and reduces cerebral infarction in rats exposed to transient focal cerebral ischemia. This treatment was effective in the rats when applied before or one hour after the ischemic insult. (Aarts et al. Science 298:846-850 2002) also discloses the research described in US Patent Application 2003 0050243 A1.
As is exemplified by the examples listed above, the majority of known methods for modification of NMDA receptors generally involve administration of receptor antagonists which inhibit receptor function completely. The instant inventors are the first to modify the NMDAR by inhibiting the interaction of the unique domain of the tyrosine kinase Src enzyme with NADH dehydrogenase subunit 2 (ND2); thus preventing Src upregulation of the NMDAR by preventing binding between Src and ND2.
SUMMARY OF THE INVENTION
Src-mediated upregulation of NMDAR activity is prevented by peptide fragments of the Src unique domain and by a unique domain-binding antibody (Yu et al. Science 275:674-678 1997; Lu et al. Science 279:1363-1368 1998) leading to the hypothesis that the upregulation of NMDAR function by Src depends on an interaction between a region in the unique domain of Src and an unknown protein in the NMDAR complex (Ali et al. Current Opinion in Neurobiology 11:336-342 2001). In order to test the hypothesis, the instant inventors searched for proteins that may interact with the unique domain of Src and may thereby mediate the interaction between this kinase and NMDARs. These proteins were generally termed “SUDAPIs” (Src unique domain anchoring protein inhibitors) by the instant inventors since they anticipate that other such inhibitors may exist which exhibit identical functions.
As a result of their search, the instant inventors became the first to identify NADH dehydrogenase subunit 2 (ND2; nucleotide sequence SEQ ID NO:8 and amino acid sequence SEQ ID NO:9) as a Src unique domain-interacting protein (Gingrich et al. PNAS 101(16):6237-6242 2004). ND2 functions as an adapter protein anchoring Src to the NMDAR complex, thus permitting Src-mediated upregulation of NMDAR activity. The instant inventors identified a region of the Src unique domain which interacts with ND2; a region located approximately at amino acid positions 40-49 of the Src protein (SEQ ID NO:1). The exogeneous peptide inhibits the ability of ND2 to anchor the Src protein to the NMDAR complex. This peptide, approximately 10 amino acids in length, has been named “SUDAPI-1” by the instant inventors, since it is the first such peptide discovered which functions to inhibit the Src unique domain anchoring protein. Administration of this exogeneous peptide prevents ND2 interaction with the Src unique domain; thus inhibiting Src-mediated upregulation of NMDAR activity. Since this peptide alone cannot cross the cell membrane to enter the cellular interior, it is combined with a carrier capable of penetrating the cell membrane. Illustrative, albeit non-limiting examples of carriers are peptides derived from viral transduction domains, such as the TAT domain derived from the Human Immunodeficiency Virus (HIV) and VP22 derived from the Herpes Simplex Virus, arginine-rich peptides, fusogenic antennapedia peptides derived from Drosophilia and lipids. Lipids can facilitate crossing of the cell membrane by enclosing the peptide in a lipid vesicle or liposome (lipid transfection protocol) or the peptide can be directly modified with lipid groups. Use of the HIV-Tat domain peptide as a carrier is exemplified in the Examples described herein. SUDAPI-1 fused to the HIV-Tat domain is designated “TSUDAPI-1” (SEQ ID NO:2). The NMDAR activity is evoked by glutamate and is additionally regulated by many distinct pathways other than the Src pathway. Inhibition of Src suppresses but does not completely inhibit the NMDAR as is apparent from the electrophysiologic measurements of receptor activity shown in FIGS. 5D-F . Thus, the instant invention provides methods and compositions for modifying NMDAR function without completely blocking the receptor or adversely affecting other neuronal proteins with the use of generalized kinase inhibitors. These methods and compositions may be used to ameliorate diseases and/or other conditions related to NMDAR signaling. Illustrative, albeit non-limiting examples of such diseases and/or other conditions are stroke, hypoxia, ischemia, multiple sclerosis, Huntington's chorea, Parkinson's disease, Alzheimer's disease, hyperglycemia, diabetes, traumatic injury, epilepsy, grand mal seizures, spasticity, cerebral palsy, asthma, cardiac arrest, macular degeneration, mental diseases, schizophrenia, AIDS dementia complex, other dementias, AIDS wasting syndrome, inflammation, pain, opioid addiction, cocaine addiction, alcohol addiction, other conditions associated with substance abuse and anorexia. An example of such amelioration is illustrated in Example 7 wherein pain behaviors are reduced in rats treated with the composition of the instant invention prior to undergoing the formalin test. Furthermore, in addition to reducing inflammatory pain, the composition of the instant invention inhibits Src-mediated NMDAR upregulation-dependent neuropathic pain in rats and mice having peripheral nerve injury (Example 9).
Src upregulation of the NMDAR is involved in the pathway of long-term potentiation (LTP)(Huang et al. Neuron 29:485-496 2001; Lu et al. Science 279:1363-1367 1998). Since LTP is considered a model for learning and memory, the compositions of the instant invention are contemplated for use in methods which elucidate mechanisms of learning and memory and/or enhance learning and memory.
The NMDAR is expressed almost exclusively in neurons; however the interaction between Src and ND2 was shown to occur in multiple and diverse tissues (Example 8 and FIGS. 10A-B ). Thus, the instant inventors hypothesize that the Src-ND2 interaction has functions other than regulation of NMDAR's and contemplate that the compositions of the instant invention can be used in methods for the general inhibition of Src in multiple cell types.
Accordingly, it is an objective of the instant invention to provide a method for modifying NMDAR interaction with non-receptor tyrosine kinase Src in any cell which expresses the NMDAR by providing a composition including at least one SUDAPI and administering the composition to the cell in an amount effective to achieve modification of the NMDAR interaction with non-receptor tyrosine kinase Src in the cell wherein said modification ameliorates a disease or condition related to NMDAR signaling. The methods and compositions of the instant invention are particularly suited to use with cells of the nervous system but can also be used with any cell which expresses the NMDAR.
It is another objective of the instant invention to provide a pharmaceutical composition for modifying NMDAR interaction with non-receptor tyrosine kinase Src in cells comprising at least one SUDAPI combined with a pharmacologically acceptable solution or carrier.
It is also an objective of the instant invention to provide a method for modifying NMDAR interaction with non-receptor tyrosine kinase Src in any cell which expresses the NMDAR by providing a composition including SUDAPI-1 and administering the composition to the cell in an amount effective to achieve modification of the NMDAR interaction with non-receptor tyrosine kinase Src in the cell wherein said modification ameliorates a disease or condition related to NMDAR signaling.
It is another objective of the instant invention to provide a pharmaceutical composition for modifying NMDAR interaction with non-receptor tyrosine kinase Src in cells comprising SUDAPI-1 combined with a pharmacologically acceptable solution or carrier.
It is yet another objective of the instant invention to provide a method for modifying NMDAR interaction with non-receptor tyrosine kinase Src in any cell which expresses the NMDAR by providing a composition including TSUDAPI-1 and administering the composition to the cell in an amount effective to achieve modification of the NMDAR interaction with non-receptor tyrosine kinase Src in the cell wherein said modification ameliorates a disease or condition related to NMDAR signaling.
It is still another objective of the instant invention to provide a pharmaceutical composition for modifying NMDAR interaction with non-receptor tyrosine kinase Src in cells comprising TSUDAPI-1 combined with a pharmacologically acceptable solution.
It is another objective of the instant invention to provide an isolated peptide (ND2.1; SEQ ID NO:7) which interacts with the Src unique domain to anchor Src to the NMDAR complex thus permitting Src-mediated upregulation of NMDAR activity.
It is still another objective of the instant invention to provide a method for inhibiting non-receptor tyrosine kinase Src in cells expressing non-receptor tyrosine kinase Src by providing a composition including at least one SUDAPI and administering the composition to the cells in an amount effective to achieve inhibition of non-receptor tyrosine kinase Src in the cells.
It is another objective of the instant invention to provide a pharmaceutical composition for inhibiting non-receptor tyrosine kinase Src in cells comprising at least one SUDAPI combined with a pharmacologically acceptable solution or carrier.
It is another objective of the instant invention to provide a composition useful in methods for elucidating the mechanisms of learning and memory.
It is yet another objective of the instant invention to provide a composition useful in methods for enhancing learning and memory.
It is another objective of the instant invention to provide a composition useful in methods for treating inflammatory pain.
It is yet another objective of the instant invention to provide a composition useful in methods for treating neuropathic pain.
Another objective of the instant invention is to provide a method for ameliorating inflammatory and/or neuropathic pain in a subject by modifying NMDAR interaction with non-receptor tyrosine kinase Src in any subject having cells which express the NMDAR by providing a composition including at least one SUDAPI and administering the composition to the subject in an amount effective to achieve modification of the NMDAR interaction with non-receptor tyrosine kinase Src in the cells to ameliorate pain in the subject.
It is yet another objective of the instant invention to provide a method for ameliorating inflammatory and/or neuropathic pain in a subject by modifying NMDAR interaction with non-receptor tyrosine kinase Src in cells of the subject by providing a composition including SUDAPI-1 (SEQ ID NO:1) or TSUDAPI-1 (SEQ ID NO:2) and administering the composition to the subject in an amount effective to achieve modification of the MNDAR interaction with non-receptor tyrosine kinase Src in the cells to ameliorate pain in the subject.
Other objectives and advantages of the instant invention will become apparent from the following description taken in conjunction with the accompanying drawings wherein are set forth, by way of illustration and example, certain embodiments of the instant invention. The drawings constitute a part of this specification and include exemplary embodiments of the present invention and illustrate various objects and features thereof.
ABBREVIATIONS AND DEFINITIONS
The following list defines terms, phrases and abbreviations used throughout the instant specification. Although the terms, phrases and abbreviations are listed in the singular tense the definitions are intended to encompass all grammatical forms.
As used herein, the term “subject” refers to any organism having cells which express or are capable of expressing NMDA receptors.
As used herein, the term “modification” refers to any action and/or treatment which alters the function of a protein.
As used herein, the term “inhibition” refers to any action and/or treatment which operates against the full activity of a protein thus reducing and/or completely suppressing protein function.
As used herein, the term “interaction” refers to an action wherein two substances in close physical proximity act upon each other.
As used herein, the term “anchor” means to stabilize or secure firmly in place.
As used herein, the term “isolated peptide” refers to a peptide which has been “altered by the hand of man” and separated from the co-existing materials of its natural state. An isolated peptide has been changed or removed from its original environment or both.
As used herein, the abbreviation “CNS” refers to the central nervous system, which includes the brain, cranial nerves and the spinal cord.
As used herein, the abbreviation “PNS” refers to the peripheral nervous system, which is the network of nerves that connect the CNS to organs, muscles, vessels and glands. Peripheral nerve injury often results in abnormal neuropathic pain, hyperalgesia and/or allodynia.
As used herein, the term “excitatory neurotransmission” refers the passage of signals from one neuron to another via chemical substances or electrical impulses.
As used herein, the abbreviation “NMDAR” refers to the N-methyl-D-aspartate receptor, an ionotropic cation-ion specific, ligand-gated (glutamate-gated) ion channel which is activated by NMDA or NMDA-like ligands (agonist activation) such as glutamate. The NMDAR is a multi-protein complex including the core channel subunits with associated scaffolding and regulatory proteins, located in the excitatory synapses in the post-synaptic density. Activation of the receptor opens the channel to allow cations (Ca +2 , Na + and K + ) to cross the cellular membrane. “Upregulation of NMDAR activity” refers to the enhanced opening of the receptor ion channels.
As used herein, the term “Src” refers to a protein exhibiting tyrosine-specific kinase activity. The Src protein is involved in controlling diverse cellular functions, including regulation of NMDAR activity.
As used herein, the term “phosphorylation” refers to a reversible covalent modification wherein a phosphate group (non-protein) is attached/detached to a protein. The addition and removal of the phosphate group causes changes in the tertiary structure of the protein that alter its activity.
As used herein, the abbreviation “PSD” refers to the post-synaptic density, a specialized portion of the neuronal cytoskeleton, located near the post-synaptic membrane. The PSD provides a support matrix for signal transduction.
As used herein, the abbreviation “LTP” refers to long term potentiation, an activity-dependent persistent enhancement of synaptic transmission which is considered a model of learning and memory. The biochemical signaling cascade which results in LTP involves the activation of Src which in turn, activates NMDARs.
As used herein, the abbreviation “ND2” refers to NADH dehydrogenase subunit 2, a subunit of mitochondrial Complex I. The instant inventor was the first to recognize that ND2 is present in the PSD and acts as an adaptor protein for anchoring Src to the NMDAR complex.
As used herein, the abbreviation “SUDAPI” refers to any substance which functions as a Src unique domain anchoring protein inhibitor.
As used herein, the abbreviation “SUDAPI-1” refers to the first Src unique domain anchoring protein inhibitor discovered by the instant inventors. SUDAPI-1 is a peptide, generally 10 amino acid residues in length corresponding approximately to amino acid positions 40-49 of the Src unique domain (SEQ ID NO:1).
As used herein, the phrase “corresponding approximately to amino acid positions 40-49 of the Src unique domain” refers to the slight difference which is possible in amino acid position numbering of the Src protein due to species variations and conventions within the art regarding whether the first methionine counts as a residue or not.
As used herein, the abbreviation “TSUDAPI-1” refers to SUDAPI-1 which is combined with the carrier peptide, HIV-Tat (SEQ ID NO:2).
As used herein, the term “carrier” refers to any substance which is attached to another substance which alone cannot traverse the cell membrane to enter the cellular interior. The carrier substance functions to carry this other substance through the cellular membrane into the cellular interior. Illustrative, albeit non-limiting examples include lipids and peptides having transducing and/or fusogenic ability.
As used herein, the term “HIV-Tat” refers to the transduction domain of the human immunodeficiency virus (HIV); the causative agent of Acquired Immunodeficiency Syndrome (AIDS). HIV-Tat peptide is often used as a carrier to transport molecules into cells.
As used herein, the term “VP22” refers to a transduction domain of the herpes simplex virus. VP22 peptide is often used as a carrier to transport molecules into cells.
As used herein, the term “antennapedia” refers to peptides derived from Drosophilia which have fusogenic ability. Antennapedia peptide is often used as a carrier to transport molecules into cells.
The phrase “pharmaceutically acceptable” is used herein as described in U.S. Pat. No. 6,703,489. “Pharmaceutically acceptable” means approved by a regulatory agency or listed in a generally approved pharmacopeia for use in animals and humans. Solutions are usually preferred when a composition is administered intravenously. Illustrative, albeit non-limiting examples of pharmaceutically acceptable solutions include water, oils, saline, aqueous dextrose and glycerol.
As used herein, the phrase “amount effective” refers to an amount of a composition sufficient to elicit a change in activity of the NMDAR.
As used herein, the phrase “ameliorate a disease and/or condition” refers to an action which causes symptoms of a disease and/or condition to improve or become better.
As used herein, the phrase “ameliorating pain” refers to an action which causes pain symptoms to improve and/or disappear.
As used herein, the abbreviation “SH” refers to a Src homology domain; regions that have been used to define highly-conserved protein modules found in a wide variety of signaling proteins (T. Pawson Nature 373:573-580 1995).
As used herein, the phrase “unique domain” refers to a Src domain having low sequence conservation and unknown function.
As used herein, the abbreviation “ND4” refers to NADH degydrogenase subunit 4, an oxidoreductase protein, a component of mitochondrial Complex I (J E Walker Quarterly Reviews of Biophysics 25(3):253-324 1992; Sazanov et al. Biochemistry 39:7229-7235 2000; Sazanov et al. Journal of Molecular Biology 302:455-464 200).
As used herein, the abbreviation “NdufA9” refers to NADH-Ubiquinone Oxidoreductase 1 alpha subcomplex 9, also a subunit of mitochondrial complex I (NCBI GeneID:4704).
As used herein, the abbreviation “Cyto 1” refers to cytochrome c oxidase subunit 1, an inner mitochondrial membrane protein that is part of Complex IV (Marusich et al. Biochim. Biophys. Acta 1362:145-159 1997).
As used herein, the abbreviation “mEPSCs” refers to miniature excitatory post-synaptic currents, a type of excitatory neurotransmission.
The terms “SUDAPI-1” and “Src40-49” are used interchangeably herein (SEQ ID NO:1).
The terms “TSUDAPI-1”; “Src40-49-Tat”; “Src40-49-HIV-Tat”; “Tat-Src40-49” and “HIV-Tat-Src40-49” are used interchangeably herein (SEQ ID NO:2).
The terms “Src40-58” and “scrambled Src40-58” are used repeatedly throughout and refer to peptides comprising amino acid residues 40-58 of SEQ ID NO:4.
The term “Src49-58” is used repeatedly throughout and refers to a peptide comprising amino acid residues 49-58 of SEQ ID NO:4.
As used herein, the term “pain” refers to an unpleasant sensation. Pain has both physical and emotional components. Pain is mediated by nerves which carry the pain impulses to the brain where their interpretation can be influenced by many factors.
As used herein, the term “inflammatory pain” refers to pain associated with inflammation. Inflammation is the nonspecific immune response of an organism to infection, irritation and/or injury. Inflammation is characterized by redness, swelling, warmth and pain. The formalin test as performed on rats in Example 7 is a model for inflammatory pain.
As used herein, the term “neuropathic pain” refers to pain directly associated with the nervous system resulting from damage to the nerves or other changes in the nervous system. Neuropathic pain is associated with changes in sensory processing (for example, with temperature and touch) and occurs without inflammation. The cuff-implantation in mice as exemplified in Example 9 is a model for neuropathic pain.
As used herein, the term “allodynia” refers to pain caused by a stimulus that does not normally result in a pain response. Allodynia involves a change in the quality of a sensation or a loss of specificity of a sense, i.e. a first response to a stimulus is not pain, but a next response to the stimulus results in pain. Tactile allodynia is pain that results from a non-injurious stimulus to the skin, such as a light touch.
As used herein, the abbreviation “PWT” refers to paw withdrawal threshold, a measurement of pain sensitivity in animals, in particular, rats and mice. Threshold is measured in terms of force. A reduction in threshold suggests the development of allodynia.
As used herein, the term “nociceptor” refers to a specialized type of nerve cell that senses and responds to pain.
As used herein, the term “hyperalgesia” refers to a condition of altered perception such that stimuli which would normally induce a trivial discomfort cause significant pain. Hyperalgesia can be caused by damage to nociceptors present in tissue.
As used herein, the term “transgenic animal” refers to an animal whose genome has been manipulated, such as an animal having DNA derived from a different organism, multiple copies of an endogeneous gene or having a gene disruption.
As used herein, the term “wild-type animal” refers to an animal having a natural genome without any modifications. Wild-type animals are usually used as control animals in experiments using transgenic varieties of the animal.
BRIEF DESCRIPTION OF THE FIGURES
The instant patent or application file contains at least one drawing executed in color. Copies of the patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
FIGS. 1A-E show the results of experiments evidencing that ND2 is a Src unique domain-interacting protein. FIG. 1A is a schematic diagram illustrating the domain structure of ND2, clones isolated from the yeast two-hybrid screen, and recombinant GST-tagged fusion proteins. FIG. 1B shows a blot of ND2-GST fusion proteins probed with biotinylated Src unique domain followed by a streptavidin-HRP conjugate. FIG. 1C shows a blot of ND2.1-GST probed with biotinylated domains of Src and Fyn followed by streptavidin-HRP conjugate. FIG. 1D shows immunoblots of co-immunoprecipitates from brain homogenate probed with anti-ND2, anti-Src or anti-Fyn. FIG. 1E shows an immunoblot of co-immunoprecipitates from cultured Src +/+ and Src −/− fibroblasts probed with anti-ND2.
FIGS. 2A-E show the results of experiments evidencing that ND2 is present at the post-synaptic density. FIG. 2A shows immunoblots of PSD proteins probed with anti-ND2, anti-cytochrome c oxidase I (Cyto 1), anti-ND4, anti-PSD95, anti-NR1, anti-Src and anti-synaptophysin. FIG. 2B shows immunoblots of mitochondrial proteins prepared by differential centrifugation probed with anti-ND2, anti-Cyto 1 and anti-ND4. FIG. 2C shows immunoblots of PSD proteins showing the specificity of the N-terminal ND2 antibody by pre-adsorption with the antigenic peptide used to derive the antibody. FIG. 2D shows immunoblots of PSD and mitochondrial proteins probed with two independent rabbit polyclonal antibodies directed against two disparate regions of ND2. FIG. 2E shows three representative post-embedding immunogold electron microscopy images of rat hippocampus CA1 synapses, pre-synaptic. Scale bar is 200 nm.
FIGS. 3A-B show the results of experiments evidencing that ND2 interacts with Src at the post-synaptic density. FIG. 3A shows immunoblots of co-immunoprecipitates from PSD preparations probed with anti-ND2 or anti-Src. FIG. 3B shows recombinant ND2.1-GST fusion protein, but not ND2.2-GST, ND2.3-GST, or GST alone, pulls Src from PSD preparations.
FIGS. 4A-G show the results of experiments evidencing that ND2 interacts with Src at the NMDAR complex. FIG. 4A shows immunoblots of co-immunoprecipitates from PSD preparations probed with anti-ND2 or with anti-NMDA receptor subunit 1 (NR1). FIG. 4B shows an immunoblot of co-immunoprecipitates from PSD preparations using anti-GluR2 anti-GABA A Rα, anti-GABA A Rβ2/3 and anti-Kv3.1 antibodies to immunoprecipitate. FIG. 4C shows a dot blot of ND2-GST fusion proteins probed with biotinylated Src40-58 or scrambled Src40-58 peptides followed by streptavidin-HRP conjugate. FIG. 4D shows a blot of ND2.1-GST probed with boptinviated Src unique domain in the presence of either Src40-58 or scrambled Src40-58 peptides followed by streptavidin-HRP conjugate. FIG. 4E shows immunoblots of co-immunoprecipitates obtained from PSD proteins in the presence of either Src40-58 or scrambled Src40-58 probed with anti-ND2 or stripped and re-probed with anti-Src. FIG. 4F , left panel shows immunoblots of co-immunoprecipitates obtained from PSD proteins in the presence of either Src40-58 or scrambled Src40-58. FIG. 4F , right panel shows immunoblots of co-immunoprecipitates obtained from PSD proteins in the presence of GST-ND2.1 fusion protein probed with anti-Src or anti-NR1. FIG. 4G shows immunoblots of co-immunoprecipitates obtained from PSD proteins in the presence of either Src40-58 or scrambled Src40-58 peptides probed with anti-ND2 or stripped and re-probed with anti-NR1.
FIGS. 5A-F show the results of experiments evidencing that blocking expression of ND2 prevents Src-dependent regulation of NMDA receptor activity. FIG. 5A shows immunoblots of total soluble protein obtained from cultured rat hippocampal neurons treated with 50 μg/ml chloramphenicol for 48 hours and probed with anti-ND2, anti-NR1 and anti-Src. FIG. 5B shows an immunoblot of co-immunoprecipitates obtained from cultured hippocampal neurons, either treated or untreated with 50 μg/ml chloramphenicol for 48 hours and probed with anti-NR1 or anti-Src. FIG. 5C shows summary histograms (left panel) of ATP level or mitochondrial membrane potential (ΔψM), as assessed by TMRM fluorescence dequenching (right panel), in cultured hippocampal neurons either untreated or treated 50 μg/ml chloramphenicol for 48 hours. FIG. 5D shows that the upregulation of NMDAR activity in the presence of the Src activator peptide EPO(pY)EEIPIA (SEQ ID NO:5), labeled as (pY)EEI (amino acid residues 4-7 of SEQ ID NO:5), is prevented in neurons treated with chloramphenicol for 48 hours. FIG. 5E shows that the reduction of NMDA activity in the presence of the Src40-58 peptide is also prevented in neurons treated with chloramphenicol for 48 hours. FIG. 5F shows a summary histogram of electrophysiology data. FIG. 5F shows amino acid residues 4-7 of SEQ ID NO:5 (pY) EEI.
FIGS. 6A-C show the results of experiments evidencing that the Src40-49 (SUDAPI-1) peptide specifically interacts with the ND2.1 peptide. FIG. 6A is a schematic diagram depicting the Src40-58, Src40-49, Src49-58, and scrambled Src40-58 peptides. FIG. 6B shows the blot of the ND2.1-GST fusion protein which was probed with biotinylated Src peptides followed by streptavidin-HRP conjugate. FIG. 6C shows the dot blots of ND2.1-GST fusion proteins probed with biotinylated Src peptides followed by streptavidin-HRP conjugate.
FIGS. 7A-D show results of experiments showing the effects of TSUDAPI-1 on 2.5% formalin-induced flinching or biting/licking behaviors. FIG. 7A shows the cumulative flinches in different phases observed within the hour. P 1 represents a time period of 0-8 minutes; P 2 A represents a time period of 12-28 minutes and P 2 B represents a time period of 32-60 minutes. Values depict means (n=7, Src40-49Tat; n=20, saline). P<0.05, P<0.01 with student t test compared to saline control. FIG. 7B shows measurement of flinching behaviors observed within an hour. FIG. 7C shows the cumulative biting/licking behaviors in different phases observed within the hour. FIG. 7D shows measurement of the time of each biting/licking behavior observed within an hour.
FIGS. 8A-D show results of experiments showing the effects of HIV-TAT on 2.5% formalin-induced flinching or biting/licking behaviors. FIG. 8A shows the cumulative flinches in different phases observed within the hour. P 1 represents a time period of 0-8 minutes; P 2 A represents a time period of 12-28 minutes and P 2 B represents a time period of 32-60 minutes. Values depict means (n=7, HIV-Tat; n=20, saline). P<0.05, P<0.01 with student t test compared to saline control. FIG. 8B shows measurement of flinching behaviors observed within an hour. FIG. 8C shows the cumulative biting/licking behaviors in different phases observed within the hour. FIG. 8D shows measurement of the time of each biting/licking behavior observed within an hour.
FIGS. 9A-B show SEQ ID NOS:6 and 7; FIG. 9A shows the nucleotide sequence encoding recombinant ND2.1 protein (SEQ ID NO:6); FIG. 9B shows the amino acid sequence of recombinant ND2.1 protein (SEQ ID NO:7).
FIGS. 10A-B show immunoblots evidencing that ND2 and Src interact in multiple, diverse tissues. FIG. 10A shows immunoblots of co-immunoprecipitates from various tissues and FIG. 10B shows immunoblots of co-immunoprecipitates from tissue homogenates probed with anti-ND2, anti-Src, or anti-Fyn. Tissues: B—brain; H—heart; I—intestine; K—kidney; Liv—liver; Lu—lung; P—pancreas; Sk—skeletal muscle; Sp—spleen and T—testis.
FIG. 11 shows graphs evidencing that intrathecal injection of 0.02 pmol of Src40-49TAT (TSUDAPI-1, SEQ ID NO:2) significantly reverses allodynia in rats.
FIG. 12 shows graphs evidencing that intravenous injection of 10 pmol/g of Src40-49TAT (TSUDAPI-1, SEQ ID NO:2) significantly reverses allodynia in rats.
FIG. 13 shows graphs evidencing that intravenous injection of 100 pmol Src40-49TAT (TSUDAPI-1, SEQ ID NO:2) significantly reverses allodynia in wild type mice but does not further increase paw withdrawal threshold (PWT) in Src null mice.
FIGS. 14A-D show data illustrating the increase in tyrosine phosphorylation of the NR2B subunit after formalin injection (inflammatory pain model) and further show that this increase of NR2B tyrosine phosphorylation is significantly reduced by intrathecal administration of Src40-49Tat (SEQ ID NO:2). FIG. 14A shows a western blot of an immunoprecipitation using an anti-NR2B antibody and an anti-phosphorylated tyrosine antibody. FIG. 14B shows a graph quantifying the tyrosine phosphorylation calculated as a percent of the control. This data was calculated prior to formalin injection and at three times post-infection; at 5 minutes, 30 minutes and 60 minutes. FIG. 14C shows another western blot of an immunoprecipitation using an anti-NR2B antibody and an anti-phosphorylated tyrosine antibody. This blot evidences the reduction of formalin-induced tyrosine phosphorylation resulting from treatment with Src40-49Tat (SEQ ID NO:2) and the absence of reduction resulting from treatment with scrambled Src40-49Tat (sSrc40-49Tat). FIG. 14D shows a graph quantifying the tyrosine phosphorylation (after treatment with Src40-49Tat or sSrc40-49) calculated as a percent of the control.
FIGS. 15A-B show data illustrating the increase in tyrosine phosphorylation of the NR2B subunit in animals having a cuff implant (neuropathic pain model) and further show that this increase of NR2B tyrosine phosphorylation is significantly reduced by intrathecal administration of Src40-49Tat (SEQ ID NO:2). FIG. 15A shows a western blot of an immunoprecipitation using an anti-NR2B antibody and anti-phosphorylated tyrosine antibody. FIG. 15B shows a graph quantifying the tyrosine phosphorylation calculated as a percent of the control. This graph represents quantification of band (from western blots) density in three experiments.
FIGS. 16A-E show the results of experiments evidencing that an antibody against ND2 recognizes NADH-Ubiquinone Oxidoreductase 1 alpha subcomplex 9 (NdufA9), a subunit of mitochondrial complex I (NCBI GeneID:4704). FIG. 16A shows immunoblots of PSD proteins probed with anti-ND2, anti-cytochrome c oxidase I (Cyto 1), anti-NdufA9, anti-PSD95, anti-NR1, anti-Src and anti-synaptophysin. FIG. 16B shows immunoblots of mitochondrial proteins prepared by differential centrifugation probed with anti-ND2, anti-Cyto 1 and anti-NdufA9. FIGS. 16C-E are identical to FIGS. 2C-E .
DETAILED DESCRIPTION OF THE INVENTION
Example 1
NADH dehydrogenase subunit 2 (ND2) is a Src unique domain-binding protein.
A yeast two-hybrid screen of a fetal brain library using bait constructs containing the murine Src unique domain was conducted in order to search for proteins that interact with the Src unique domain.
cDNAs encoding amino acids 4-82 (the Src unique domain) and amino acids 4-150 (the Src unique and SH3 domains) of murine n-Src were ligated into pEG202 (Gyuris et al. Cell 75:791-803 1993) to create two expression vectors encoding in frame LexA fusions containing the Src unique domain (the nucleotide sequence encoding Src is SEQ ID NO:3 and the amino acid sequence is SEQ ID NO:4). The bait constructs were then sequenced. Both baits were tested to ensure that the baits did not activate transcription of the reporters in the absence of prey and that both could enter the nucleus and bind to LexA operators. To create the selection strains for screening, each bait plasmid was individually transformed into the yeast strain EGY48. EGY48 has an integrated Leu2 selectable marker regulated by 6 LexA operator repeats, and carries a reporter plasmid with the lacZ gene regulated by 8 LexA operator repeats. Bait-prey interactions that occur with low affinity result in activation of the Leu2 reporter gene only, whereas high affinity interactions result in activation of both the Leu2 and lacZ reporter genes, allowing for double selection of prey. The selection strain was transformed with a representative activation-tagged cDNA prey fusion library constructed using ˜1 kilobase EcoRI fragmented poly A(+) RNA from human fetal brain. Yeast transformed with the prey library (approximately 1.1×10 6 clones) were screened by double selection on X-gal Leu − medium. Prey cDNAs encoding proteins that interacted with the bait were isolated and sequenced.
Src, Fyn, and ND2 recombinant proteins were prepared. The cDNAs encoding the SH3 and SH2 domains of mouse n-Src and Fyn were PCR subcloned, ligated in frame into pGEX4T-1 (Amersham Pharmacia Biotech, Baie d'Urfé, Québec), and sequenced. These plasmids, as well as plasmids encoding the unique domains of Src and Fyn in pGEX2T'6, were transformed into BL21 bacteria, and GST fusion proteins were purified by glutathione affinity chromatography. To create the ND2.1, ND2.2, and ND2.3 GST fusion proteins, cDNAs encoding amino acids 239-321 (ND2.1-GST; SEQ ID NO:7), amino acids 189-238 (ND2.2-GST; SEQ ID NO:11), and amino acids 1-188 (ND2.3-GST; SEQ ID NO:13) of human ND2 were PCR subcloned and ligated into pGEX4T-1 (the nucleotide sequence encoding ND2 is SEQ ID NO:8 and the amino acid sequence is SEQ ID NO:9; the nucleotide sequences encoding ND2.1; ND2.2 and ND2.3 are SEQ ID NOS:6, 10 and 12, respectively). Using PCR-based single nucleotide mutagenesis, all cDNAs encoding ND2 fusion proteins were corrected for differences between mitochondrial and nuclear codons to prevent premature translation termination and protein truncation. All constructs were then confirmed by sequencing. The plasmids were transformed into bacteria, and GST fusion proteins were purified by glutathione affinity chromatography.
Detailed protocols for in vitro binding assays, pull down assays, immunoblotting, and co-immunoprecipitation techniques can be found in Pelkey et al. (Neuron 34:127-138 2002).
In two independent screens, cDNA fragments encoding overlapping regions within NADH dehydrogenase subunit 2 (ND2) were isolated ( FIG. 1A ). ND2 is a 347 amino acid protein (SEQ ID NO:9) that is a subunit of the inner mitochondrial membrane enzyme, NADH dehydrogenase (Complex I). ND2 is one of a group of seven oxidoreductase proteins that are encoded in the mitochondrial genome and which co-assemble with 35 nuclear encoded subunits to form Complex I. ND2 on its own lacks enzymatic activity (J. E. Walker Quarterly Reviews of Biophysics 25(3):253-324 1992; Sazanov et al. Journal of Molecular Biology 302:455-464 2000; Sazanov et al. Biochemistry 39:7229-7235 2000). FIG. 1A is a schematic diagram illustrating the domain structure of ND2, clones isolated from the yeast two hybrid screen, and recombinant GST-tagged fusion proteins. The lines point out the beginning of the oxidoreductase domain at amino acid position 23 and the end at amino acid position 197. Each clone and GST-fusion protein represent overlapping regions within ND2.
As yeast two-hybrid screening may reveal false positive protein-protein interactions, the interaction between Src and ND2 was observed using an independent methodological approach. Direct binding in vitro between ND2 and Src was tested using recombinant proteins. A series of GST fusion proteins comprised of portions of ND2 that spanned the overlapping region found with the yeast two-hybrid screen were made ( FIG. 1A ). Importantly, the cDNAs encoding each of the ND2 fusion proteins were corrected for differences between mitochondrial and nuclear codons so that the sequence of the ND2 portion of the fusion proteins was that which would have been produced by translation in the mitochondria. For example, FIG. 9A shows the nucleotide sequence encoding recombinant ND2.1 protein (SEQ ID NO:6). Codons that are highlighted with bold type were altered by PCR-based single nucleotide mutagenesis. TGA was changed to TGG to prevent premature translation termination and protein truncation. GAA was changed to GAG to remove a restriction enzyme site. Numbers in parenthesis correspond to equivalent positions in the endogenous human ND2 nucleotide sequence. FIG. 9B shows the amino acid sequence of recombinant ND2.1 protein (SEQ ID NO:7). Numbers in parenthesis correspond to equivalent positions in the endogenous human ND2 amino acid sequence. Each of the series of GST-fusion proteins was tested individually for interaction with the Src unique domain (“pull-down” assay). FIG. 1B shows a blot of ND2-GST fusion proteins probed with biotinylated Src unique domain followed by a streptavidin-HRP conjugate. A GST fusion protein containing amino acids 239-321 of ND2 (ND2.1-GST; SEQ ID NO:7) was found that bound to the unique domain of Src ( FIG. 1B ). In contrast, GST fusion proteins containing amino acids 189-238 (ND2.2-GST) or 1-188 (ND2.3-GST) of ND2 (ND2 protein sequence is SEQ ID NO:9) did not bind to the Src unique domain. These results, together with those from the yeast two-hybrid screen, indicate that ND2 is a Src unique domain-binding protein. The results indicate further that the Src-binding portion of ND2 is contained within the region of amino acids 239-321 (SEQ ID NO:7). This region of ND2 shows little conservation amongst the mitochondrially encoded oxidoreductase proteins and is outside the so-called “oxidoreductase domain”, a signature region identified in all mitochondrially encoded subunits of NADH dehydrogenase (J. E. Walker Quarterly Reviews of Biophysics 25(3):253-324 1992; Sazanov et al. Journal of Molecular Biology 302:455-464 2000; Sazanov et al. Biochemistry 39:7229-7235 2000) and some antiporters (Fearnley et al. Biochim. Biophys. Acta 1140:105-143 1992).
Another “pull-down” assay was conducted to determine whether the binding of ND2 might generalize to other domains of Src or to other Src family tyrosine kinases.
However, it was found that ND2.1-GST did not bind to either of the prototypic protein-protein interaction domains of Src, the SH2 or SH3 domains ( FIG. 1C ). FIG. 1C shows a blot of ND2.1-GST probed with biotinylated domains of Src and Fyn followed by streptavidin-HRP conjugate.
To examine the potential interaction of ND2 with other kinases of the Src family recombinant domains of Fyn were tested, the protein most closely related to Src but which has little primary sequence conservation in the unique domain (Brown et al. Biochim. Biophys. Acta 1287:121-149 1996; T. Pawson Nature 373:573-580 1995). It was found that ND2.1-GST did not interact in vitro with the Fyn unique domain; nor did ND2.1 bind to the SH2 or SH3 domains of Fyn. Thus, the ND2.1 region does not interact with the SH2 or SH3 domains of Src or Fyn nor does it generally bind to the unique domain of Src family tyrosine kinases.
To investigate the possibility that Src and ND2 may interact in vivo, brain lysates were immunoprecipitated with antibodies directed against ND2 (anti-ND2) or against Src (anti-Src). It was found that immunoprecipitating Src led to co-immunoprecipitation of ND2 ( FIG. 1D ). FIG. 1D shows immunoblots of co-immunoprecipitates from brain homogenate probed with anti-ND2, anti-Src or anti-Fyn as indicated. Non-specific IgG was used as a negative control for immunoprecipitation. Fyn was readily detected in the brain homogenate used as a starting material for the co-immunoprecipitation (data not illustrated). Conversely, immunoprecipitating with anti-ND2 resulted in co-immunoprecipitation of Src. In contrast, anti-ND2 did not co-immunoprecipitate Fyn and neither ND2 nor Src was immunoprecipitated with a non-specific IgG ( FIG. 1D ). As an independent immunoprecipitation control it was found that ND2 was co-immunoprecipitated by anti-Src from Src +/+ fibroblasts but not from Src −/− fibroblasts ( FIG. 1E ). FIG. 1E shows an immunoblot of co-immunoprecipitates from cultured Src +/+ and Src −/− fibroblasts probed with anti-ND2. Non-specific IgG was used as a negative control for immunprecipitation, and immunoblotting of ND2 protein from both cell lines was used as a positive control. Thus, in addition to finding the ND2-Src unique domain interaction in two yeast two-hybrid screens and in vitro binding assays with recombinant proteins, it was found that ND2 and Src co-immunoprecipitated with each other, which together led to the conclusion that the ND2 is a Src unique-domain binding protein that may interact with Src in vivo.
Example 2
ND2 is present in post-synaptic densities in brain.
Post-synaptic density proteins (Kennedy et al. Proceedings of the National Academy of Science USA 80:7357-7361 1983) were prepared from rat brain as described in detail (Pelkey et al. Neuron 34:127-138 2002). Cellular fractionation of rat brain tissue into nuclear, heavy mitochondrial, light mitochondrial, microsomal, and cytosolic fractions was performed by differential centrifugation of tissue homogenate in 0.25 M sucrose/10 mM HEPES-NaOH, 1 mM EDTA, pH 7.4 with 2 μg each of aprotinin, pepstatin A, and leupeptin (Sigma, St. Louis, Mo.) at 4° C. Nuclei were pelleted by centrifugation at 1 000 g for 10 minutes, the supernatant was removed and spun at 3 000 g for 10 minutes to obtain a heavy mitochondrial pellet. The supernatant was removed and spun at 16 000 g for 15 minutes to obtain a light mitochondrial pellet. The supernatant was removed and spun at 100 000 g for 1 hour to obtain a microsomal pellet and the cytosolic fraction. All pellets were then resuspended in RIPA buffer (50 mM Tris pH 7.6, 150 mM NaCl, 1 mM EDTA, 1% NP-40, 2.5 mg/ml NaDOC, 1 mM Na 3 VO 4 1 mM PMSF, and 2 μg/ml each of protease inhibitors). The light mitochondrial fraction was used in subsequent experiments. For Western blots, 50 μg of total protein was loaded per lane, resolved by SDS-PAGE, transferred to nitrocellulose membranes, and probed with anti-ND2, anti-Cytol and anti-ND4 (mouse monoclonals, Molecular Probes Inc., Eugene, Oreg.), anti-PSD95 (mouse monoclonal clone 7E3-1B8, Oncogene Research Products, Cambridge, Mass.), anti-NR1 (mouse monoclonal clone 54.1, Pharmingen), anti-Src, or anti-synaptophysin (mouse monoclonal, Sigma).
Post-embedding immunogold electron microscopy was carried out. Sprague Dawley rats were anesthetized and perfused with 4% paraformaldehyde plus 0.5% glutaraldehyde in 0.1 M phosphate buffer. Parasagittal sections of the hippocampus were cryoprotected in 30% glycerol and frozen in liquid propane. Frozen sections were immersed in 1.5% uranyl acetate in methanol at −90° C., infiltrated with Lowicryl HM-20 resin at −45° C., and polymerized with ultraviolet light. Sections were incubated in 0.1% sodium borohydride plus 50 mM glycine in TBS and 0.1% Triton X-100 (TBST), followed by 10% normal goat serum (NGS) in TBST, primary antibody in 1% NGS in TBST, and immunogold (10 nm; Amersham Pharmacia Biotech) in 1% NGS in TBST plus 0.5% polyethylene glycol. Finally, the sections were stained in uranyl acetate and lead citrate prior to analysis.
In the CNS a prominent subcellular location for Src is in the post-synaptic density (PSD) (Yu et al. Science 275:674-678 1997), a subsynaptic specialization at glutamatergic synapses comprised of α-amino-3-hydroxy-5-methylisoxazolepropionic acid (AMPA-) and NMDA-type glutamate receptors together with scaffolding, signaling and regulatory proteins (Walikonis et al. Journal of Neuroscience 20:4069-4080 2000). Because Src is known to regulate subsynaptic NMDARs (Yu et al. Science 275:674-678 1997), if ND2 is the protein mediating the interaction between NMDARs and the unique domain of Src then ND2 is predicted to be present in the PSD. This was tested by preparing PSD proteins from rat brain homogenates by sequential fractionation and determining whether ND2 was present in this fraction. Characteristic of a bona fide PSD fraction, the fraction which was prepared contained post-synaptic proteins including PSD-95 and NMDA receptor subunit proteins but lacked the pre-synaptic protein synaptophysin ( FIG. 2A ). FIG. 2A shows immunoblots of PSD proteins probed with anti-ND2, anti-cytochrome c oxidase I (Cyto 1), anti-ND4, anti-PSD95, anti-NR1, anti-Src and anti-synaptophysin as indicated. It was found that ND2 was present in the PSD fraction and the amount of ND2 estimated in this fraction was approximately 15% of that in the total brain homogenate. In contrast to ND2, neither the oxidoreductase protein ND4, another mitochondrially-encoded component of Complex I (J. E. Walker Quarterly Reviews of Biophysics 25(3):253-324 1992; Sazanov et al. Journal of Molecular Biology 302:455-464 2000; Sazanov et al. Biochemistry 39:7229-7235 2000) nor cytochrome c oxidase subunit 1 (Cyto 1), an inner mitochondrial membrane protein that is part of Complex IV (Marusich et al. Biochim. Biophys. Acta 1362:145-159 1997), was detectable in the PSD fraction. On the other hand, Cyto 1 and ND4, as well as ND2, were readily detected in proteins from brain mitochondria ( FIG. 2B ). Subsequent investigation indicated that the NdufA9 (NADH-ubiquinone oxidoreductase 1 alpha subcomplex 9) subunit of mitochondrial complex I was detected and not ND4 ( FIG. 16B ). FIG. 2B shows immunoblots of mitochondrial proteins prepared by differential centrifugation probed with anti-ND2, anti-Cyto 1 and anti-ND4. Neither NR1 nor NR2A/B was detected in the mitochondrial fraction (data not shown).
As noted above, subsequent investigations indicated that the antibody initially thought to recognize the mitochondrial protein ND4, a control in the study, actually recognizes NADH-Ubiquinone Oxidoreductase 1 alpha subcomplex 9 (NdufA9). Like ND4, NdufA9 protein has a molecular weight of 39 kDa and is a subunit of NADH dehydrogenase (mitochondrial complex I). However, unlike ND4, NdufA9 is encoded in the nucleus. Because NdufA9 is a subunit of mitochondrial complex I, as is ND4, NdufA9 is also an appropriate control for the instantly described experiments (Gingrich et al. PNAS 103(25):9744 2006; published online on Jun. 8, 2006). Referring now to FIGS. 16A-B , characteristic of a bona fide PSD fraction, the fraction which was prepared contained post-synaptic proteins including PSD-95 and NMDA receptor subunit proteins but lacked the pre-synaptic protein synaptophysin ( FIG. 16A ) FIG. 16A shows immunoblots of PSD proteins probed with anti-ND2, anti-cytochrome c oxidase I (Cyto 1), anti-NdufA9, anti-PSD95, anti-NR1, anti-Src and anti-synaptophysin as indicated. It was found that ND2 was present in the PSD fraction. In contrast to ND2, neither the NADH-Ubiquinone Oxidoreductase 1 alpha subcomplex 9 (NdufA9), a subunit of mitochondrial complex I, nor the cytochrome c oxidase subunit 1 (Cyto 1), an inner mitochondrial membrane protein that is part of Complex IV (Marusich et al. Biochim. Biophys. Acta 1362:145-159 1997), were detectable in the PSD fraction. On the other hand, Cyto 1 and NdufA9, as well as ND2, were readily detected in proteins from brain mitochondria ( FIG. 16B ). FIG. 16B shows immunoblots of mitochondrial proteins prepared by differential centrifugation probed with anti-ND2, anti-Cyto 1 and anti-NdufA9. FIGS. 16C-E are identical to FIGS. 2C-E .
Although the molecular size of the protein detected by anti-ND2 in the PSD preparation matched that of ND2 in mitochondria, it is conceivable that the protein detected in the PSD preparation was not ND2 but a protein of the same molecular size that was recognized by anti-ND2. However, it was found that incubating anti-ND2 with the antigen to which the antibody was raised prevented the immunoblotting signal ( FIG. 2C ). FIG. 2C shows immunoblots of PSD proteins showing the specificity of the N-terminal ND2 antibody by pre-adsorption with the antigenic peptide used to derive the antibody. Morever, it was found that a separate antibody directed towards a distinct epitope in a region of ND2 remote from that of the anti-ND2 epitope also detected ND2, at the correct molecular size, in the PSD preparation, as well as in the mitochondrial preparation ( FIG. 2D ). FIG. 2D shows immunoblots of PSD and mitochondrial proteins probed with two independent rabbit polyclonal antibodies directed against two disparate regions of ND2. The N-terminal ND2 antibody was used for all subsequent experiments illustrated. Thus, ND2 was found in the PSD preparation by two separate antibodies, and this could not be accounted for by a general contamination with mitochondrial proteins because neither Cyto 1 nor ND4 were detected in the PSD.
In addition to examining PSD protein preparations, the presence of ND2 in PSDs was tested for by means of post-embedding immunogold electron microscopy in the CA1 stratum radiatum of rat hippocampus (Petralia et al. Nature Neuroscience 2:31-36 1999; Sans et al. Journal of Neuroscience 20:1260-1271 2000). With this experimental approach the tissue is fixed immediately after the animal is sacrificed and prior to sectioning so that protein localization is preserved. ND2 labeling was found, as visualized by secondary antibody conjugated to 10 nm gold particles, in the PSD and the postsynaptic membrane in dendritic spines of CA1 neurons ( FIG. 2E ), as well as over mitochondria (not illustrated). FIG. 2E shows three representative post-embedding immunogold electron microscopy images of rat hippocampus CA1 synapses, pre-synaptic. Scale bar is 200 nm. ND2 labeling was enriched in the post-synaptic membrane approximately 30-fold as compared with the plasma membrane in the remainder of the dendritic spine (0.37 particles per PSD/section versus 0.012, p<0.05) and there was no obvious accumulation of ND2 labeling along the plasma membrane of the dendritic shaft. The ND2 labeling observed in the PSD and post-synaptic membrane could not have been due to labeling in mitochondria because it is known that mitochondria are excluded from dendritic spines (Shepherd et al. Journal of Neuroscience 18(20):8300-8310 1998). Thus, these results indicate that ND2 is present in the biochemically defined PSD protein fraction and is localized at PSDs in CA1 neurons.
Example 3
ND2 interacts with Src at the NMDA receptor complex in post-synaptic densities.
Since previous results indicate that ND2 is present in PSDs from brain, it was examined whether ND2 interacts with Src in PSDs. It was found that immunoprecipitating ND2 from the PSD fraction led to co-immunoprecipitation of Src and vice versa ( FIG. 3A ), indicating that ND2 and Src interact post-synaptically at glutamatergic synapses. FIG. 3A shows immunoblots of co-immunoprecipitates from PSD preparations probed with anti-ND2 or anti-Src as indicated. Non-specific IgG (either rabbit or mouse) was used as a negative control for both antibodies. Moreover, Src was pulled from the PSD fraction by the fusion protein ND2.1-GST, but not by either ND2.2- or ND2.3-GST ( FIG. 3B ). FIG. 3B shows recombinant ND2.1-GST fusion protein, but not ND2.2-GST, ND2.3-GST, or GST alone, pulls Src from PSD preparations. Thus, as it was found with the Src-ND2 binding in vitro, these results indicate that amino acids 239-321 of ND2 (SEQ ID NO:7) are both necessary and sufficient for ND2 to interact with Src in the PSD.
The hypothesis that ND2 is the protein mediating the interaction between Src and NMDARs requires that, in addition to being present in the PSD and interacting there with Src, ND2 is part of NMDAR complex of proteins. To determine whether ND2 is a component of the NMDAR protein complex, NMDAR complexes were immunoprecipitated from the PSD fraction, using an antibody directed against the core NMDAR subunit NR1 (Dingledine et al. Pharmacology Reviews 51:7-61 1999), and the co-immunoprecipitating proteins were probed with anti-ND2. It was found that ND2 co-immunoprecipitated ( FIG. 4A ), and conversely, immunoprecipitating with anti-ND2 led to co-immunoprecipitation of NR1 ( FIG. 4A ). FIG. 4A shows immunoblots of co-immunoprecipitates from PSD preparations probed with anti-ND2 or with anti-NMDA receptor subunit 1 (NR1) as indicated. Non-specific IgG (either rabbit or mouse) was used as a negative control for both antibodies. Neither ND2 nor NR1 was immunoprecipitated by non-specific IgG, and ND2 did not co-immunoprecipitate with the potassium channel Kv3.1 ( FIG. 4B ), a negative control for non-specific immunoprecipitation of post-synaptic proteins, therefore it was concluded that ND2 is an NMDAR complex protein. FIG. 4B shows an immunoblot of co-immunoprecipitates from PSD preparations using anti-GluR2, anti-GABA A Rα, anti-GABA A Rβ2/3 and anti-Kv3.1 antibodies to immunoprecipitate. Probe was anti-ND2. Importantly, neither ND4 nor Cyto 1 was detected in co-immunoprecipitates of NR1 (not illustrated) indicating that mitochondrial proteins in general are not components of the NMDAR complex. Moreover, ND2 did not co-immunoprecipitate with GluR2, GABA A Rα or GABA A Rβ2/3 ( FIG. 4B ) indicating that ND2 is not a detectable component of AMPA receptor or γ-aminobutyric acid (GABA) receptor complexes.
Thus, while ND2 is a component of NMDAR complexes it is not generally a component of neurotransmitter receptor complexes in the brain.
Example 4
ND2 acts as an adapter protein for Src.
Src40-58 and scrambled Src peptides were biotinylated by incubating with Sulfo-NHS-Biotin (Pierce Chemical Co., Rockford, Ill.) for 30 minutes at room temperature (SEQ ID NO:4, Src protein). The biotinylation reaction was then quenched by the addition of Tris-HCl (pH 8.0) to a final concentration of 20 mM. Purified recombinant fusion proteins (˜20 μg each) were dotted onto nitrocellulose and dried overnight. Membranes were blocked with 5% BSA in PBS for 1 hour, after which biotinylated peptides (30 μg/ml) diluted 1:1000 in fresh 5% BSA in PBS were added. The membranes were incubated with the peptides for 1 hour, washed, and probed using a streptavidin-HRP conjugate. Bound probe was then detected on film using an ECL kit.
ND2 acts as an adapter protein for Src. Amino acids 40-58 (SEQ ID NO:4) within the Src unique domain have been implicated in the binding of Src to the interacting protein in the NMDAR complex (Yu et al. Science 275:674-678 1997; Lu et al. Science 279:1363-1368 1998; Yu et al. Nature 396:469-474 1998) and thus, ND2 was predicted to bind to this region of Src. This prediction was examined in vitro using a peptide with the sequence of amino acids 40-58 (Src40-58; SEQ ID NO:4) which was found to bind directly to ND2.1-GST ( FIG. 4C ) in vitro. In contrast, a peptide with identical amino acid composition, but a scrambled sequence (scrambled Src40-58), did not bind to ND2.1-GST. Neither Src40-58 nor scrambled Src40-58 bound to ND2.2-GST, ND2.3-GST or to GST alone ( FIG. 4C ). FIG. 4C shows a dot blot of ND2-GST fusion proteins probed with biotinylated Src40-58 or scrambled Src40-58 peptides followed by streptavidin-HRP conjugate. Furthermore, the effect of Src40-58 on the interaction between Src and ND2 was examined ( FIGS. 4D and 4E ). It was found that incubating ND2.1-GST with Src40-58 prevented this fusion protein from pulling down the Src unique domain protein in vitro ( FIG. 4D ). FIG. 4D shows a blot of ND2.1-GST probed with boptinylated Src unique domain in the presence of either Src40-58 or scrambled Src40-58 peptides followed by streptavidin-HRP conjugate. On the other hand, scrambled Src40-58 did not affect the interaction between the ND2.1-GST and Src unique domain proteins. Incubating PSD proteins with Src40-58 prevented the co-immunoprecipitation of ND2 by anti-Src but this was not affected by scrambled Src40-58 ( FIG. 4E ). FIG. 4E shows immunoblots of co-immunoprecipitates obtained from PSD proteins in the presence of either Src40-58 or scrambled Src40-58 probed with anti-ND2 or stripped and re-probed with anti-Src. Importantly, Src40-58 did not affect the immunoprecipitation of Src from PSDs. Thus, it was concluded that amino acids 40-58 of Src interact with the region spanned by ND2.1, thereby mediating the binding between the Src unique domain and ND2.
As ND2 alone is not catalytically active (J. E. Walker Quarterly Reviews of Biophysics 25(3):253-324 1992; Sazanov et al. Journal of Molecular Biology 302:455-464 2000; Sazanove et al. Biochemistry 39:7229-7235 2000), its functional role in the NMDAR complex was investigated. ND2 might be a phosphorylation target for Src, but it was found that ND2 immunoprecipitated from PSD protein fractions was not detectably phosphorylated on tyrosine. Moreover, inclusion of ND2.1-GST did not alter the catalytic activity of Src in vitro (not illustrated) consistent with the binding of ND2 to the unique domain rather than to the regulatory or catalytic domains. Thus, it is unlikely that ND2 is a target of Src or a regulator of Src kinase activity.
However, it was found that the co-immunoprecipitation of Src with NMDARs ( FIG. 4F , left panel) was suppressed by Src40-58, but not scrambled Src40-58, and by ND2.1 ( FIG. 4F , right panel) indicating that the association of Src with the NMDAR complexes depends on the interaction with ND2. FIG. 4F , left panel shows immunoblots of co-immunoprecipitates obtained from PSD proteins in the presence of either Src40-58 or scrambled Src40-58. FIG. 4F , right panel shows immunoblots of co-immunoprecipitates obtained from PSD proteins in the presence of GST-ND2.1 fusion protein probed with anti-Src or anti-NR1 as indicated. In contrast, the co-immunoprecipitation of ND2 with NMDARs was not affected by Src40-58 ( FIG. 4G ), implying that binding ND2 to Src is not necessary for ND2 to associate with NMDAR complexes. FIG. 4G shows immunoblots of co-immunoprecipitates obtained from PSD proteins in the presence of either Src40-58 or scrambled Src40-58 peptides probed with anti-ND2 or stripped and re-probed with anti-NR1. Taking these results together, it was concluded that ND2 may function as an adapter protein that anchors Src in the NMDAR complex.
Example 5
Loss of ND2 in neurons prevents the regulation of NMDA receptor activity by Src.
Fetal rat hippocampal neurons were prepared, cultured, and used for electrophysiological recordings 12-17 days after plating. Methods for whole cell recordings are described in Pelkey et al. (Neuron 34:127-138 2002).
It was hypothesized that if ND2 is a Src adapter protein then loss of ND2 should prevent the upregulation of NMDAR activity by endogenous Src (Yu et al. Science 275:674-678 1997). This was tested by investigating miniature excitatory post-synaptic currents (mEPSCs) recorded from cultured hippocampal neurons (MacDonald et al. Journal of Physiology (London) 414:17-34 1989). In these neurons the NMDAR-mediated component of mEPSCs is increased by activating endogenous Src with a high-affinity activating phosphopeptide EPQ(pY)EEIPIA (Liu et al. Oncogene 8:1119-1126 1993) and is reduced by applying Src40-58 (Yu et al. Science 275:674-678 1997). It is predicted that each of these effects will be lost by blocking the expression of ND2, if it acts as an adapter protein for Src in the NMDAR complex. In order to suppress ND2 expression, the hippocampal cultures were treated with chloramphenicol to selectively inhibit translation of mitochondrially encoded proteins but not translation of proteins encoded in the nucleus (Ibrahim et al. Journal of Biological Chemistry 251:108-115 1976). After 48 hours treatment with chloramphenicol it was found that the level of ND2 in the cultures was reduced by more than 95% whereas there was no significant change in the levels of the nuclear encoded proteins examined ( FIG. 5A ). FIG. 5A shows immunoblots of total soluble protein obtained from cultured rat hippocampal neurons treated with 50 μg/ml chloramphenicol for 48 hours and probed with anti-ND2, anti-NR1 and anti-Src as indicated. Importantly, chloramphenicol did not affect the level of Src or of the NMDAR subunit NR1 but did suppress the co-immunoprecipitation of Src with the NMDAR complex ( FIG. 5B ), as predicted if ND2 is an adapter protein linking Src to the complex. FIG. 5B shows an immunoblot of co-immunoprecipitates obtained from cultured hippocampal neurons, either treated or untreated with 50 μg/ml chloramphenicol for 48 hours and probed with anti-NR1 or anti-Src.
The effect of the 48 hours treatment with chloramphenicol on the ATP levels, mitochondrial membrane potential, viability and general functioning of the hippocampal neurons in culture was examined. It was found that chloramphenicol did not significantly affect the level of ATP levels in the cultures ( FIG. 5C ), consistent with the lack of effect of chloramphenicol treatment for up to 55 hours on ATP levels in other cell types in culture (Ramachandran et al. Proceedings of the National Academy of Science USA 99:6643-6648 2002). FIG. 5C shows summary histograms (left panel) of ATP level or mitochondrial membrane potential (ΔψM), as assessed by TMRM fluorescence dequenching (right panel), in cultured hippocampal neurons either untreated or treated 50 μg/ml chloramphenicol for 48 hours. To examine the effect of chloramphenicol on mitochondrial membrane potential (ΔψM) in individual neurons, the dequenching of the potentiometric fluorescent cationic dye tetramethylrhodamine methyl ester (TMRM) by the mitochondrial uncoupler carbonyl cyanide p-trifluoromethoxyphenylhydrazone (FCCP) was monitored (Reers et al. Biochemistry 30:4480-4486 1991). The dequenching response evoked by bath-applied FCCP (2 μM) in neurons from chloramphenicol-treated or control cultures was assessed. It was found that the dequenching response of chloramphenicol-treated neurons was not different from that of untreated neurons ( FIG. 5C ), indicating that ΔψM was not affected by chloramphenicol. Moreover, it was found that neurons treated with chloramphenicol were not distinguishable from untreated neurons in terms of cell number, gross morphology, resting membrane potential, resting intracellular calcium concentration, action potential amplitude, or mEPSC frequency (data not illustrated). Thus, from these data together it was concluded that treatment with chloramphenicol for 48 hours did not detectably compromise the functioning of the neurons. Nevertheless, it was noted that the intracellular solution used for all whole-cell recordings contained 2 mM Mg-ATP, so that the level of intracellular ATP was equal in all cells throughout the experiments.
In neurons treated with chloramphenicol for 48 hours it was found that the NMDAR component of the mEPSCs was not affected by administering either the EPQ(pY)EEIPIA (SEQ ID NO:5) peptide or the Src40-58 peptide ( FIGS. 5D-F ). In contrast, in control experiments administering EPQ(pY)EEIPIA (SEQ ID NO:5) increased the NMDAR component of mEPSCs by 172±28% and application of Src40-58 decreased the NMDAR component to 56±4% ( FIGS. 5D-F ). Chloramphenicol was present during the recording periods of the control experiments and therefore the loss of effect of the EPQ(pY)EEIPIA (SEQ ID NO:5) and Src40-58 peptides cannot be attributed to an acute effect of chloramphenicol. FIG. 5D shows that the upregulation of NMDAR activity in the presence of the Src activator peptide EPQ(pY)EEIPIA (SEQ ID NO:5), labeled as (pY)EEI (amino acid residues 4-7 of SEQ ID NO:5), is prevented in neurons treated with chloramphenicol for 48 hours. FIG. 5E shows that the reduction of NMDA activity in the presence of the Src40-58 peptide is also prevented in neurons treated with chloramphenicol for 48 hours. Composite traces are shown in black, the NMDAR component in dark grey, and the AMPAR component in light grey. Scale bars are 50 ms/10 pA. FIG. 5F shows a summary histogram of electrophysiology data. NMDA component data were calculated as Q 20′ /Q 2′ , and AMPA component data were calculated as A 20′ /A 2′ . A 48 hour chloramphenicol treatment prevents the modulation of NMDAR function by the Src activator peptide (SEQ ID NO:5) and Src40-58 peptides, while neither of these reagents affected the AMPA receptor component of the MEPSCs under the recording conditions used. An * indicates a significant difference, Student's t-test, p<0.05. Taking our results together, it is concluded that Src-dependent regulation of the activity of NMDARs depends on expression of ND2 through its anchoring of Src to the NMDAR complex.
Example 6
Src40-49 interacts directly with ND2
To detect the binding of ND2.1-GST with Src peptides, the ND2.1-GST fusion protein was purified on glutathione SEPHAROSE. Src40-58, Src40-49, Src49-58, and scrambled Src40-58 peptides (30 mg/ml; synthesized by HSC Peptide Synthesis Facility; all four peptides are schematically depicted in FIG. 6A ) were biotinylated by incubating with Sulfo-NHS-Biotin (Pierce Chemical Co., Rockford, Ill.) for 30 minutes at room temperature. The biotinylation reaction was then quenched by the addition of Tris-HCl (pH 8.0) to a final concentration of 20 mM. Biotinylated peptides were incubated with ND2.1-GST on beads for 1 hour at 4° C. The beads were washed three times with PBS/0.1% Triton X-100, then resuspended in PBS+SDS-PAGE sample buffer. After brief centrifugation, samples were resolved by SDS-PAGE, transferred to nitrocellulose membranes, and probed using a streptavidin-HRP conjugate (Sigma, St. Louis, Mo.). Bound probe was then detected on film using an ECL kit (Amersham Pharmacia Biotech, Baie d'Urfé, Québec). FIG. 6B shows the blot of the ND2.1-GST fusion protein which was probed with biotinylated Src peptides followed by streptavidin-HRP conjugate.
Src40-58, Src40-49, Src49-58, scrambled Src40-58, TAT-Src40-49, and scrambled TAT-Src40-49 peptides were biotinylated by incubating with Sulfo-NHS-Biotin (Pierce Chemical Co., Rockford, Ill.) for 30 minutes at room temperature. The biotinylation reaction was then quenched by the addition of Tris-HCl (pH 8.0) to a final concentration of 20 mM. Purified recombinant fusion proteins (˜20 μg each) were dotted onto nitrocellulose and dried overnight. Membranes were blocked with 5% BSA in PBS (pH 7.5) for 1 hour, after which biotinylated peptides (30 μg/ml) diluted 1:1000 in fresh 5% BSA in PBS were added. The membranes were incubated with the peptides for 1 hour, washed, and probed with streptavidin-HRP conjugate. Bound probe was then detected on film using an ECL kit. FIG. 6C shows the dot blots of ND2.1-GST fusion proteins probed with biotinylated Src peptides followed by streptavidin-HRP conjugate.
Example 7
TAT-Src40-49 (TSUDAPI-1) reduces pain behavior
Male Sprague-Dawley rats 150-200 g were used for all experiments. Rats were housed in pairs, maintained on a 12/12 hour light/dark cycle, and allowed free access to food and water. All experiments were conducted during 10 am and 5 μm.
Peptide Src40-49Tat (TSUDAPI-1; SEQ ID NO:2) or Tat alone (amino acid residues 1-11 of SEQ ID NO:2) was dissolved in sterilized saline. Peptide or saline was injected intravenously at a volume 1 ml/Kg into rat's tail 45 minutes before behavioral testing. Injections were done under brief halothane anesthesia and rats were returned to the cages after injections.
The formalin test was performed as previously described (Liu et al. European Journal of Pharmacology 408(2):143-152 2000). Rats were placed in a plexiglass observation chamber for an initial 20 minutes to allow acclimatization to the testing environment. Formalin 2.5% was injected subcutaneously in a volume of 50 ml into the plantar aspect of the hind paw. Following injections, rats were returned to the observation chamber and monitored for flinching behaviors (lifting, shaking and overt flinching with a ripple over the haunch) and biting/licking time. Two rats in adjacent chambers were observed at one time, with observations occurring in alternate 2 minute bins. Recorded episodes were not corrected, thus values represent about half of the total behaviors expressed.
FIGS. 7A-D show the effect of Src40-49Tat (0.1 pmol) on 2.5% formalin induced flinching or biting/licking behaviors. Peptides or saline controls were injected 45 minutes before behavioral testing. FIG. 7B shows measurement of flinching behaviors observed within an hour. FIG. 7A shows the cumulative flinches in different phases observed within the hour. P 1 represents a time period of 0-8 minutes; P 2 A represents a time period of 12-28 minutes and P 2 B represents a time period of 32-60 minutes. Values depict means (n=7, Src40-49Tat; n=20, saline). P<0.05, P<0.01 with student t test compared to saline control. FIG. 7D shows measurement of the time of each biting/licking behavior observed within an hour. FIG. 7C shows the cumulative biting/licking behaviors in different phases observed within the hour. P 1 represents a time period of 0-8 minutes; P 2 A represents a time period of 12-28 minutes and P 2 B represents a time period of 32-60 minutes. Values depict means (n=7, Src40-49Tat; n=20, saline). P<0.05, P<0.01 with student t test compared to saline control.
FIGS. 8A-D show the effect of HIV-Tat (1 pmol/g) on 2.5% formalin induced flinching or biting/licking behaviors. Peptides or saline controls were injected 45 minutes before behavioral testing. FIG. 8B shows measurement of flinching behaviors observed within an hour. FIG. 8A shows the cumulative flinches in different phases observed within the hour. P 1 represents a time period of 0-8 minutes; P 2 A represents a time period of 12-28 minutes and P 2 B represents a time period of 32-60 minutes. Values depict means (n=7, HIV-Tat; n=20, saline). P<0.05, P<0.01 with student t test compared to saline control. FIG. 8D shows measurement of the time of each biting/licking behavior observed within an hour. FIG. 8C shows the cumulative biting/licking behaviors in different phases observed within the hour. P 1 represents a time period of 0-8 minutes; P 2 A represents a time period of 12-28 minutes and P 2 B represents a time period of 32-60 minutes. Values depict means (n=7, HIV-Tat; n=20, saline). P<0.05, P<0.01 with student t test compared to saline control. As compared to HIV-Tat alone and the saline control, the Src40-49Tat peptide is shown to reduce pain behaviors over a time period of an hour.
It is known that tyrosine phosphorylation of the NR2 subunits plays a key role in NMDA receptor activation (Moon et al. PNAS USA 91:3954-3958 1994; Lau et al. Journal of Biological Chemistry 270:20036-20041 1995; Xiong et al. Journal of Neuroscience 19:RC37(1-6) 1999). It is also known that inflammatory hyperalgesia is associated with rapid and prolonged enhancement of tyrosine phosphorylation of the NR2B subunits of NMDA receptors (Guo et al. The Journal of Neuroscience 22(14):6208-6217 2002). Thus, considering that protein phosphorylation is a major mechanism for both normal and pathological receptor function, the effect of the formalin test on receptor phosphorylation was examined.
FIGS. 14A-D illustrate the increase in tyrosine phosphorylation of the NR2B subunit after formalin injection ( FIGS. 14A-B ) and further illustrate that this increase of NR2B tyrosine phosphorylation is significantly reduced by intrathecal (i.t.) administration of Src40-49Tat (SEQ ID NO:2) ( FIGS. 14C-D ). FIG. 14A shows a western blot of an immunoprecipitation using an anti-NR2B antibody and an anti-phosphorylated tyrosine antibody. It can be seen that by 60 minutes post-injection of formalin, tyrosine phosphorylation of the NR2B subunit increases. FIG. 14B shows a graph quantifying the tyrosine phosphorylation calculated as a percent of the control. This data was calculated prior to formalin injection and at three times post-injection; at 5 minutes, 30 minutes and 60 minutes. As can be seen, the amount of NR2B subunit that is phosphorylated peaks at around 30 minutes post-injection. FIG. 14C shows another western blot of an immunoprecipitation using an anti-NR2B antibody and an anti-phosphorylated tyrosine antibody. This blot evidences the reduction of formalin-induced tyrosine phosphorylation resulting from treatment with Src40-49Tat (SEQ ID NO:2) and the absence of reduction resulting from treatment with scrambled Src40-49Tat (sSrc40-49Tat). FIG. 14D shows a graph quantifying the tyrosine phosphorylation (after treatment with Src40-49Tat or sSrc40-49) calculated as a percent of the control. This data was calculated at 60 minutes post-injection of formalin to treated animals.
Example 8
ND2-Src interaction in multiple tissues
Total soluble protein was prepared from pre-weighed rat tissues by homogenization at 4° C. in 0.25 M sucrose/10 mM HEPES-NaOH, 1 mM EDTA, pH 7.4 with 2 μg/ml each of aprotinin, pepstatin A, and leupeptin. Following brief configuration of the samples at 4 000 g, NP-40 was added to 1% (vol/vol) to the cleared supernatants. After incubation for 10 minutes, the protein concentration of the samples was determined by detergent compatible protein assay (BioRad Laboratories, Mississauga, Ontario) and equilibrated. The solubilized proteins were centrifuged briefly at 14 000 g to remove insoluble material and then incubated with 5 μg of either anti-ND2 (rabbit polyclonal from Dr. R. F. Doolittle, UCSD, CA; described in Mariottini et al. PNAS USA 83:1563-1567 1986), anti-Src (mouse monoclonal clone 327 from J. Bolen, DNAX, Palo Alto, Calif.) or control, non-specific rabbit or mouse IgG (Sigma) overnight at 4° C. Immune complexes were isolated by the addition of 10 μl of protein G-SEPHAROSE beads followed by incubation for 2 hours at 4° C. Immunoprecipitates were then washed three times with RIPA buffer, re-suspended in RIPA buffer+SDS-PAGE sample buffer and boiled for 5 minutes. The samples were resolved by SDS-PAGE, transferred to nitrocellulose membranes and analyzed by immunoblotting with anti-ND2, anti-Src or anti-Fyn (mouse monoclonal clone 25, Pharmingen, Mississauga, Ontario). Bound antibody was then detected on film using appropriate secondary antibody/HRP conjugates and an ECL kit (Amersham Pharmacia Biotech). For control immunoprecipitations under denaturing conditions, SDS was added to the initial protein samples to a final concentration of 0.4% and the samples were boiled for 5 minutes and rapidly cooled to 4° C. prior to the addition of the antibodies used for immunoprecipitation. In addition, pre-adsorption of the anti-ND2 antibody with antigenic peptide prevented antibody signal detection on immunoblots.
Non-receptor tyrosine kinase Src and ND2 are both expressed in cells of multiple, diverse tissues. Illustrative, albeit non-limiting, examples are peripheral nervous system tissue, central nervous system tissue, heart, intestine, kidney, liver, lung, pancreas, skeletal muscle, spleen, testis, bone, skin and brain. The data presented in FIGS. 10A-B shows that ND2 and Src interact in multiple, diverse tissues. Immunoblots of co-immunoprecipitates from various tissues ( FIG. 10A ) and tissue homogenates ( FIG. 10B ) probed with anti-ND2, anti-Src, or anti-Fyn as indicated. Tissues: B—brain; H—heart; I—intestine; K—kidney; Liv—liver; Lu—lung; P—pancreas; Sk—skeletal muscle; Sp—spleen and T—testis. Non-specific IgG applied to liver homogenate was used as a negative control for co-immunoprecipitation. Immunoblotting of Fyn protein from brain was used as a positive control for the anti-Fyn antibody. In these experiments the cell lysates were prepared using non-denaturing conditions, but when denaturing conditions were used to prepare the proteins, no co-immunoprecipitation of Src by anti-ND2 or of anti-Src was found (data not illustrated).
Example 9
Src40-49Tat (TSUDAPI-1) inhibits neuropathic pain
Increased activity of NMDA receptors is known to play a major role in pain produced by peripheral nerve injury (Ren et al. Journal of Orofacial Pain 13:155-163 1999). This type of pain is debilitating and treatments remain relatively ineffective. Antagonists of the NMDA receptor complex have been suggested as potential drugs for neuropathic pain management (Planells-Cases et al. Mini Review of Medicinal Chemistry 3(7):749-756 2003). However, non-selective blocking of NMDA receptor function is deleterious, since complete blockade of synaptic transmission mediated by NMDA receptors is known to hinder neuronal survival (Ikonomidou et al. Lancet: Neurology 1:383-386 2002; Fix et al. Experimental Neurology 123:204 1993; Davis et al. Stroke 31:347 2000; Morris et al. Journal of Neurosurgery 91:737 1999). The method of the instant invention selectively blocks NMDAR-mediated excitatory post-synaptic current (EPSC) without effecting the AMPA (GluR1-containing α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid) component.
Pain induced by cuff implantation, in a laboratory animal such as a rat or mouse, is an art-accepted model of neuropathic pain. Generally, in cuff implantation a nerve root in the sciatic nerve leading to a hind paw is tied off by surgical implantation of a “cuff”, for example, a polyethylene ring. Over a period of time the nerve degenerates and a neuropathic pain pattern develops. A control is created by subjecting another group of animals to “sham surgery”, a procedure wherein the animals receive the same type of surgery as cuff implantation without the physical implantation of the cuff. After a period of time, the paw is stimulated by a series of filaments or exposure to a small amount of moderate heat. Pain is measured by observation of “paw withdrawal”, in general, if the animal lifts the paw and the time it takes to do so. Typically, an animal not experiencing neuropathic pain will not respond to the stimuli. When testing using filaments, threshold is defined in terms of force. A reduction in threshold suggests the development of allodynia. This testing method is described in the art; Ren Physiological Behavior 67:711-716 1999 and Guo et al. The Journal of Neuroscience 22(14):6208-6217 2002.
In this experiment, tactile allodynia was induced in a group of mice by cuff implantation and symptoms were observed as early as day 3 post-surgery. Allodynia was allowed to fully develop at 8-10 days post-surgery before the “paw withdrawal” tests were performed. A group of mice received an intrathecal (introduced into the space under the arachnoid membrane of the brain or spinal cord) injection of 0.02 pmol of Src40-49Tat (TSUDAPI-1, SEQ ID NO:2), a second group of mice received an intrathecal injection of 0.02 pmol Scramble Src40-49Tat and a third group of mice received an intrathecal injection of saline. “Scramble Src40-49Tat” refers to TSUDAI-1 (SEQ ID NO:2) having a “scrambled” sequence, i.e. having amino acid residues out of order from the normal. The results are presented in FIG. 11 . Green represents Src40-49Tat (TSUDAPI-1, SEQ ID NO:2), grey represents Scramble Src40-49Tat and red represents saline. Src40-49Tat (TSUDAPI-1, SEQ ID NO:2), but not Scramble Src40-49Tat or saline, significantly reversed allodynia. The reversal effect was observed as early as one hour following administration. The reversal was significant at more than 5 hours post injection, with PWT 6.03±1.45 g (Src40-49Tat) versus 1.7±0.47 g (scrambled Src40-49Tat)(p<0.05).
Another group of mice received an intravenous injection of 10 pmol/g of Src40-49Tat (TSUDAPI-1, SEQ ID NO:2) and a second group of mice received an intravenous injection of saline. The results are presented in FIG. 12 . Green represents Src40-49Tat (TSUDAPI-1, SEQ ID NO:2) and red represents saline. Src40-49Tat (TSUDAPI-1, SEQ ID NO:2), but not saline, significantly reversed allodynia. The reversal effect was observed as early as one hour following administration. The anti-allodynic effect of the peptide (SEQ ID NO:2) peaked at 2 hours following injection, with PWT 9.28±2.55 g (Src40-49Tat) versus 1.95±0.617 g (saline) (p<0.05).
Protein phosphorylation is a major mechanism for receptor function. It is known that tyrosine phosphorylation of the NR2 subunits plays a key role in NMDA receptor activation (Moon et al. PNAS USA 91:3954-3958 1994; Lau et al. Journal of Biological Chemistry 270:20036-20041 1995; Xiong et al. Journal of Neuroscience 19:RC37(1-6) 1999). It is also known that inflammatory hyperalgesia is associated with rapid and prolonged enhancement of tyrosine phosphorylation of the NR2B subunits of NMDA receptors (Guo et al. The Journal of Neuroscience 22(14):6208-6217 2002).
In this experiment, a significant increase of tyrosine phosphorylation of NMDA receptor NR2B subunits in spinal cord dorsal horn tissue was observed in cuffed rats but not in sham-operated rats ( FIG. 15A ). Intrathecal injection of 0.02 pmol Src40-49Tat (TSUDAPI-1, SEQ ID NO:2) significantly reversed the increase in tyrosine phosphorylation ( FIG. 15B ). FIG. 15A shows a western blot of an immunoprecipitation using an anti-NR2B antibody and anti-phosphorylated tyrosine antibody. FIG. 15B shows a graph quantifying the tyrosine phosphorylation calculated as a percent of the control. This graph represents quantification of band (from western blots) density in three experiments.
Another experiment was performed to compare cuff-induced allodynia in wild-type mice to Src kinase null mice (Src kinase knock-out mice). The results are shown in FIG. 13 . The PWT was tested in the mice prior to surgery. The basal PWT in Src kinase null mice was not different from that of wild-type mice; see black bars in graphs in center and right hand side in FIG. 13 , Src−/− and Src+/+. Both groups of mice received an intravenous injection of 100 pmol of Src40-49Tat (TSUDAPI-1, SEQ ID NO:2). Allodynia was depressed in Src kinase null mice throughout the testing time course, with PWT 0.01±1.53 g (wild) versus 0.21±0.04 g (null) (p<0.05) at 22 days post surgery (left graph in FIG. 13 ). Treatment with Src40-49Tat (100 pmol, intravenous injection) significantly reversed allodynia in wild-type mice from 0.008±0.0 g to 0.23±0.05 g (p<0.05), but did not further increase PWT in null mice. Nerve-injury induced increase in phosphorylation of the NR2B subunit was found to be depressed in both wild-type and Src kinase null mice. Treatment with Src40-49Tat did not further decrease phosphorylation of NR2B subunits in Src kinase null mice.
Thus, the instant inventors concluded that loss of Src or depressed action of Src through treatment with Src40-49Tat (TSUDAPI-1, SEQ ID NO:2) inhibits Src-mediated NMDAR up-regulation dependent neuropathic pain.
IN SUMMARY
The main criteria for identifying ND2 as the protein mediating the interaction between NMDARs and the unique domain of Src, as inferred from previous work (Ali et al. Current Opinion in Neurobiology 11:336-342 2001; Yu et al. Science 275:674-678 1997) are as follows: ND2 must bind directly to the unique domain of Src through amino acids 40-58 (specifically 40-49; SEQ ID NO:1); this binding must be prevented by the Src40-58 (specifically 40-49) peptide; ND2 must be present at excitatory synapses and must be a component of the NMDAR complex; and lack of ND2 must prevent the upregulation of NMDAR activity by endogenous Src.
ND2 was first considered as a potential Src unique domain-binding protein when overlapping clones of ND2 in two separate yeast two-hybrid experiments were isolated. Subsequently, the direct interaction of the Src unique domain and ND2 was confirmed through in vitro binding assays using recombinant proteins. Through these experiments the ND2.1 region was identified as necessary and sufficient for interacting with the Src unique domain. ND2.1 bound directly to the Src40-58 (specifically 40-49) peptide and the in vitro binding of the Src unique domain to ND2.1 was prevented by Src40-58 (specifically 40-49). Src and ND2 co-immunoprecipitated with each other in brain homogenates and PSD protein preparations. The co-immunoprecipitation was prevented by Src40-58 (specifically 40-49), implying that the Src-ND2 interaction identified in vitro may occur in vivo. In addition to finding ND2 in PSD protein preparations, ND2-immunoreactivity was found by immunogold electron microscopy in PSDs in the CA1 hippocampus. Moreover, co-immunoprecipitation experiments indicated that ND2 is a component of the NMDAR complex and that the Src-ND2 interaction is required for the association of Src, but not ND2, with NMDARs. It was found that depleting ND2 suppresses Src association with the NMDAR complex and prevents the upregulation of NMDAR function by activating endogenous Src at excitatory synapses. Src40-49 (SUDAPI-1; SEQ ID NO:1) was identified as the specific peptide that interacts with ND2 as Src50-58 alone did not interact with ND2. Finally, it was found that TAT-Src40-49 (TSUDAPI-1; SEQ ID NO:2) as administered to rats reduced pain behavior in the formalin test. These multiple, converging lines of evidence lead to the conclusion that ND2 is the protein mediating the interaction between NMDARs and the unique domain of Src.
ND2 is mitochondrially encoded and translated, and yet it is found within the PSDs of glutamatergic synapses in the brain. The other mitochondrial proteins examined, ND4 and Cyto 1, were not detected in the PSD fraction implying that this fraction is not contaminated non-specifically by mitochondrial proteins. Further, ND2-immunoreactivity by immunogold electron microscopy was found within structurally-identified PSDs in dendritic spines of CA1 neurons. In this preparation, proteins are immobilized by tissue fixation precluding the possibility that ND2 could have relocated from the mitochondria to the PSD during processing. Moreover, because dendritic spines are devoid of mitochondria (Shepherd et al. Journal of Neuroscience 18(20):8300-8310 1998) the ND2 immunoreactivity cannot be accounted for by mitochondria abutting the PSD. Taken together these findings indicate that ND2, but not the entire Complex I, is normally present within the PSD. The PSD contains many enzymes that may be involved in regulating synaptic functioning (P. Siekevitz Proceedings of the National Academy of Science USA 82:3494-3498 1985) including glycolytic enzymes capable of generating ATP (Wu et al. Proceedings of the National Academy of Science USA 94:13273-13278 1997). However, without other components of Complex I it is unlikely that ND2 functions catalytically within the PSD.
Thus, in addition to its localization in mitochondria and function as a component of Complex I, the present results indicate that ND2 has a second location and function in outside the mitochondria. Mitochondria are intimately linked to overall cellular functioning through generation of ATP by oxidative phosphorylation. Mitochondria are also known to be key for sequestration of intracellular calcium (D. D. Friel Cell Calcium 28:307-316 2000; R. Rizzuto Current Opinion in Neurobiology 11:306-311) and to participate in programmed cell death (Gorman et al. Developmental Neuroscience 22:348-358 2000; M. P. Mattson National Review of Molecular and Cellular Biology 1:120-129 2000). Some mitochondrial proteins are known to be present at extra-mitochondrial sites (Soltys et al. Trends in Biochemical Science 24:174-177 1999; Soltys et al. International Review of Cytology 194:133-196 1999). But, the experiments described herein indicate a new type of function for a mitochondrial protein outside this organelle, that is ND2 acts as an adapter protein that anchors Src within the NMDAR complex, where it thereby allows Src to upregulate NMDAR activity.
Upregulating the activity of NMDARs is a major function of Src in neurons in the adult CNS (Lu et al. Science 279:1363-1368 1998; Pelkey et al. Neuron 34:127-138 2002; Huang et al. Neuron 29:485-496 2001) and this mediates the induction of long-term potentiation (LTP) of excitatory synaptic transmission in CA1 neurons in the hippocampus (Ali et al. Current Opinion in Neurobiology 11:336-342 2001). The findings described herein imply that the ND2-Src interaction is essential for LTP induction as LTP in CA1 neurons is prevented by Src40-58 and by anti-Src1, an antibody that recognizes this amino acid sequence within the Src unique domain and which prevents the Src unique domain interaction with ND2.1 in vitro (J. R. G., M. W. S. unpublished observations). LTP at Schaffer collateral-CA1 synapses is the prototypic example of NMDAR-dependent enhancement of excitatory synaptic transmission, which is observed at numerous types of glutamatergic synapses throughout the CNS (Malenka et al. Science 285:1870-1874 1999). In addition, Src has been implicated in NMDAR-dependent seizures (Sanna et al. Proceedings of the National Academy of Science 97:8653-8657 2000), chronic pain (Guo et al. Journal of Neuroscience 22:6208-6217 2002) and neurotoxicity (Pei et al. Journal of Cerebral Blood Flow Metabolism 21:955-963 2001). Thus, the discovery of the Src-ND2 interaction at NMDARs, which is disclosed herein, defines a protein-protein interaction of general relevance to regulation of neuronal function, synaptic plasticity, and pathophysiology in the CNS.
Additionally, by showing an extramitochondrial action for a protein encoded in the mitochondrial genome a previously unsuspected means by which mitochondria regulate cellular function has been identified. Because ND2 and Src are broadly expressed, the interaction of ND2 with the Src unique domain may be of general relevance for control of Src signaling (Example 8 and FIGS. 10A-B ).
All patents and publications mentioned in this specification are indicative of the levels of those skilled in the art to which the invention pertains. All patents and publications are herein incorporated by reference to the same extent as if each individual publication was specifically and individually indicated to be incorporated by reference.
It is to be understood that while a certain form of the invention is illustrated, it is not to be limited to the specific form or arrangement herein described and shown. It will be apparent to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is shown and described in the specification. One skilled in the art will readily appreciate that the present invention is well adapted to carry out the objectives and obtain the ends and advantages mentioned, as well as those inherent therein. The oligonucleotides, peptides, polypeptides, biologically related compounds, methods, procedures and techniques described herein are presently representative of the preferred embodiments, are intended to be exemplary and are not intended as limitations on the scope. Changes therein and other uses will occur to those skilled in the art which are encompassed within the spirit of the invention and are defined by the scope of the appended claims. Although the invention has been described in connection with specific preferred embodiments, it should be understood that the invention as claimed should not be unduly limited to such specific embodiments. Indeed, various modifications of the described modes for carrying out the invention which are obvious to those skilled in the art are intended to be within the scope of the following claims.
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The present invention provides a method for ameliorating inflammatory and/or neuropathic pain in a subject by modifying the activity of N-methyl-D-aspartate (NMDA) receptors in cells of the subject by inhibition of the interaction of the unique domain of the tyrosine kinase Src enzyme and the NMDA receptor complex.
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This is a continuation of application Ser. No. 08/349,160, filed Dec. 2, 1994 now abandoned, which is a division of application Ser. No. 07/966,624, filed on Oct. 26, 1992 now abandoned, which is a division of application Ser. No. 07/652,158, now U.S. Pat. No. 5,200,597, issued on Apr. 6, 1993.
FIELD OF THE INVENTION
The present invention relates to systems for scanning and reading bar codes and other optically discernible symbols and, particularly, to a bar code scanner and reader system which is adapted to be hand-held and digitally controlled.
The invention is especially suitable for providing an integrated hand-held bar code scanner unit having optics and digital electronic control facilities, in an assembly adapted to high volume manufacturing techniques, and which is applicable for use with computer systems of different types from different manufacturers. Features of the invention in its optical aspects, particularly optical beam shaping and arrangement of optical elements, as well as its computerized control and motor drive systems, may find other applications in opto-electronic or photonic systems.
BACKGROUND AND SUMMARY OF THE FEATURES OF THE INVENTION
Bar code scanners produce a beam of light, often from a laser, that is appropriately shaped by beam forming optics and then scanned across a bar code symbol by a deflector such as an oscillating mirror or rotating polygon having mirror facets. Scattered light from the bar code is collected in collection optics and is incident on a photodetector in the scanner. The photodetector converts the return light into a time varying analog signal that is an electrical representation of the physical bar and space widths. Subsequent circuits convert this signal into a logic level pattern with analog timing that represents the bar code. This logic level pattern is sent to a computer and decoded to determine the characters in the message represented by the bar code. The bars and spaces are resolved by the laser spot where the scanning beam is incident on the code. Aperture stops and lenses have been used to shape the beam and the resolving spot.
Bar code scanners have used gas (HeNe lasers) that produce circular scanning spots. However, bar code symbols are often printed with low resolution printing processes, for example, using dot matrix printers, and may be subject to harsh environments or abrasion during handling. These factors cause voids to be present in the printed bars. Dust and dirt on the bars can result in obscuration of the spaces between the bars. The presence of these defects may cause reading errors.
It has been proposed to use an elongated scanning spot to decrease the probability of a reading error. The elongated, for example, elliptically shaped spot, with its major or long axis arranged parallel to the long dimension of the bars and spaces in the code, averages over the length of the bars and spaces and minimizes the effects of small defects. Anamorphic optics have been suggested for use in a bar code scanner with a gas laser which produces a circular spot in order to provide an elliptical laser spot (see, U.S. Pat. No. 4,721,860, issued Jan. 26, 1988).
Laser diodes have been used in scanners which, because their small size, as opposed to the gas laser, enables the scanner to be miniaturized. However, the beam from a laser diode is not symmetrical. For example, a visible laser diode, which is now commercially available from Toshiba (their model TOLD 9200), diverges approximately 34° in one direction and 7° in a direction orthogonal thereto. It has been proposed also, to use lenses and apertures to shape such a beam into a elliptical beam. However, such beams do not stay in the same width to height aspect ratio relationship. Rather, the beam flips so that its long dimension, initially aligned along the length of the bars, becomes oriented orthogonally to the bars of the code (see, U.S. Pat. No. 4,896,026, issued Jan. 23, 1990). The desired averaging, over the length of the bars and spaces, to minimize the effect of printing defects, is therefore not obtained throughout the working range of the scanner. Moreover, the beam becomes incapable of resolving fine (narrow or high resolution) bars and spaces. This situation can be alleviated by the use of an anamorphic optical system in which the beam is colliminated in the vertical direction (along the length of the bars of the code) and focused in the horizontal direction (see, U.S. Pat. No. 4,820,911, issued Apr. 11, 1989).
It is therefore desirable to provide a beam forming and shaping system wherein the optics provide an elongated beam which maintains its width to height aspect ratio over the entire range in front of the scanner (which may be a one to several feet long range) and is oriented with a long axis along the bars and spaces of the code and not transverse thereto. This objective has been accomplished in accordance with the invention through the use of optics which operate by diffraction and which utilize to advantage the diverging characteristics of the beam from a visible laser diode. The beam forming system of the invention has many advantages over traditional optics which are designed in accordance with geometric optic principles and which, in practice, as discussed above are subject to having the long axis of the beam flip so that the beam is no longer orientated with its long axis along the length of the bars and spaces in the code and are subject to decreased resolution and enhanced sensitivity to defects in the code.
Although there has been some statements in publications and patents that diffraction mechanisms are at work when a focused beam passes through an aperture (see A. Erteza, "Active Autofocusing Using an Aperture Gaussian Beam", Applied Optics, Volume 15, No. 9, pages 2095-2096 (September 1976) and U.S. Pat. No. 4,808,804 issued Feb. 28, 1989), it has not been appreciated how to use a diffraction mechanism and diffractive optics to advantage in shaping a beam, particularly a diverging beam from a laser diode, and maintaining it in proper orientation and aspect ratio with respect to the bars of a bar code. In addition, an optical beam shaping system in accordance with the invention requires fewer components (physical aperture stops and their supporting mechanisms can be eliminated), and the complexities of anamorphic optics are avoided.
To this end, the invention provides a system (method and apparatus) for producing a pattern of generally monochromatic light having a predetermined configuration and orientation over a range of distances in which the symbol to be recognized, for example a bar code, may be located. A diffracting element is placed in the path of the beam which forms the light in the beam in a profile having a desired configuration and orientation, preferably an elliptical configuration in which the major axis of the beam is in a direction along the bars and spaces of the code, due to far field diffraction in the range where the code is to be resolved. Far field diffraction is defined as diffraction which results beyond the Fresnel distance from the source or the exit pupil of an optical system following the source. Preferably this exit pupil is provided by a lens of short focal length which brings the end of the range where far field diffraction effects occur in the vicinity of the window of the scanner through which the beam is projected or in the vicinity of the plane closest to the scanner in which it is desired to read a coded symbol. In the far field, the beam diverges at an angle which is approximately inversely proportional to the effective aperture of the beam. This effective aperture is preferably provided at the exit pupil, defined optically in a lens which focuses the beam from the laser. If the beam diverges, as it does from a laser diode, the effective aperture will have a long dimension and a short dimension which may be oriented with respect to the bars of the code. No physical or hard aperture is required. Through the use of the lens, the Fresnel distance due to the longest dimension (length) of the aperture (since the shortest Fresnel distance is proportional to the length of the aperture squared, the Fresnel distance for the short dimension occurs before the Fresnel distance for the long dimension) is typically located inside the scanner and ahead of the scanner's window through which the beam is projected towards the code. In long range scanning applications, the Fresnel distance for the longest dimension may be located at the closest desired reading plane, which may lie exterior to the scanner. The focal length and location of the lens is adjusted with respect to the location of the laser diode and the divergence of its beam so that the effective or phantom aperture within the lens (which is located at the principal plane of the lens where the lens starts to focus the beam) is such that the aspect ratio (length to width of the elliptical beam) remains generally constant over the range where the code is located for scanning. Accordingly, far field diffraction shapes the profile of the beam into a spot of width and length where the beam is incident on the code (in the plane of the code) so as to provide the desired shape without the need for anamorphic optics and using to advantage diffraction effects, to obtain high resolution scanning. The invention does not depend upon traditional geometric optics for shaping and focusing the beam wherein diffraction effects have produced undesirable results.
The optics of a scanner, particularly the laser and its beam projecting optics which produce the outgoing beam and the detector which receives the incoming beam have traditionally been located in alignment. In order to save space and reduce the size of the scanner head and particularly the scan module in the head, the photodetector and the laser have been mounted on a plate, usually a printed circuit board in offset relationship. Then the symmetry between the incoming and outgoing beams is lost and parallax is introduced. Parallax is the difference in apparent direction of an object as seen from two different points not on a straight line with the object. In a scanning system, this translates into a nonuniformity of return signal across the scan. If the change in signal across the scan is large, the dynamic range of the electronic circuitry may not be enough to compensate for the change in signal.
It has been found in accordance with the invention that the parallax problem can be solved, even though the photodetector and the laser are physically out of alignment with each other and are spaced apart on a single board on which they are mounted. Briefly described, the arrangement utilizes a fixed mirror from which the laser beam is reflected to an optical deflector, such as an oscillatory mirror, and is projected from the deflector over a scan path with traverses a center of scan as the beam scans back and forth across the code. The mirror also collects the return light and directs it to the photodetector. The oscillatory mirror, the laser and the photodetector are arranged with respect to the fixed mirror so that the outgoing beam (when it is in the center of the scan) and the return beam travel along paths which are in the same plane. Symmetry is therefore provided between the incoming and outgoing beams and parallax is eliminated.
It has traditionally been the practice to mount the optical assembly of a scanner to the case or housing in which the scanner is contained with shock mounts; the purpose being to isolate the optical assembly from shocks which could be transmitted to the assembly if the scanner was dropped onto the floor. The assembly of the scanner with shock mounts increases its cost due to the additional cost of the shock mounts and the additional labor to install the mounts. Moreover, resonances in the mechanical system can be introduced due to the compliance of the mounts which amplifies the shock forces.
It has been found in accordance with the invention that the optical assembly can be mounted on a single board which is held in the scanner housing in tracks which may be provided by channels formed around the inside surface of the housing. The board is inserted into the channel on one-half of the housing and then into an opposing channel in an opposite half the housing when the housing is assembled by bringing the housing halves together and fastening them together by attachment devices. It has been found that this mounting arrangement is more advantageous than shock mounts in that it avoids resonances introduced by the shock mounts. The shock forces which are applied to the board via the mounts has a frequency spectrum which includes frequencies at which the mechanical system of the board and the mount are resonant. Therefore shock mounting can give rise to destructive forces. Such forces do not occur in the mounting system provided by the invention wherein the board is held in the channels in the housing halves.
Operation of a scanner involves turning the laser on and off in response to trigger signals from a switch on the scanner or from an external terminal or control computer system to which one or more scanners are connected in a network. These control computers have facilities for decoding the bar code and also for turning the scanner on and off when a code is to be read. It is desirable that the scanner be universally applicable for use with various control or host computers which may provide commands or which provide data for programming the scanner. This data may be in different formats, for example signals of different level or polarity. Heretofore, bar code scanners have been designed for compatibility with only one type of computer or with one family of computers which utilizes the same code, protocol or data format, as regards level and polarities.
It is also necessary, particularly to comply with governmental standards concerning radiological health and safety, that the laser power be regulated to be maintained within the certain power and intensity levels. In addition, there are circumstances, such as operation in high temperature environments, where the current for operating the laser increases to a level that destroys (burns up) the laser. Laser diodes are particularly sensitive to the level of current which is used to drive them and can be destroyed if the current exceeds a safe level.
Another problems arises out of the variation and intensity of the scattered light which is returned from the code. Analog automatic gain control circuits have been used to vary the gain of the preamplifiers and amplifiers following the photodetector so that the digitizer which provides the analog bar code signal does not become overloaded on the one hand or does not receive signals of such low level that they cannot be tracked and converted with high accuracy.
A still further problem is in the area of controlling the beam so that it scans at essentially constant velocity across the code. Motor control circuits have been proposed for driving motors for oscillating a mirror so as to deflect and scan the beam (see for example U.S. Pat. No. 4,496,831 issued in September 1985, wherein opposing motor drive current are controlled in an analog fashion, one for electromagnetic bias and the other for driving force generation.
Still another problem arises when there are a number of closely spaced codes on a package or sheet which must be individually read. The scan wide enough to read any one code may be positioned so as to overlap adjacent codes thereby causing misreads or erroneous reads. In addition, a wide scan, particularly from a visible laser diode, spreads the intensity over a large distance so that it may be too dim to be observed for training the beam on the code of interest. In this connection it has been proposed to use a narrow scan and, when a few bars are read, to automatically increase the scan length (see U.S. Pat. No. 4,933,538 issued Jun. 12, 1990). If the scan length is automatically increased, it still can overlap an adjacent code which is not intended to be read.
All of these problems are resolved in accordance with the invention by a digital control system utilizing a computer. The computer generates digital gain control signals depending upon the intensity of the return light detected on a scan and adjusts the gain digitally so that on a subsequent scan, the signal level is optimum. The digital gain control can be non-linear by changing the relationship between the value of the digital control signal and the intensity of the detected light in a way to more quickly bring the gain of the system to its proper value than would be the case with an analog automatic gain control system. The digital control of gain is afforded by a digitally operative potentiometer in the amplifiers which amplify the photo detected bar code signal and which can be set to provide the required resistance corresponding to a desired level of amplifier gain.
Digital control, again utilizing a digital potentiometer in a control loop, regulates the current which drives the laser so that the digital control computer can control the laser power. The laser power can be regulated to a preset value dictated by governmental health and safety regulations on initialization utilizing a digital control signal corresponding to laser output power of desired level.
The digital control computer can also generate digital control signals for operating the motor which drives the deflector (the scanning mirror). These signals may be in the form of pulses which are pulse-width modulated (vary in duration) so as to control the instantaneous velocity as well as the frequency of oscillation. The control signals also control the scan length and may be varied in response to a manual actuator which produces a signal that depends upon the pressure exerted by an operator on a trigger or control lever of the scanner. When the trigger is released or has only light pressure applied thereto, the length of the scan can be set to be quite small or stationary. This small or short scan is quite bright and enables the beam to be located on the code by visual observation of the spot of light incident on the code. Then by increasing the pressure on the trigger or control lever, the digital control signal which drives the motor changes so as to increase the scan length either linearly or non-linearly in response to pressure. The length can be increased to be just sufficient to scan the particular code of interest and not overlap any adjacent codes.
Universal operation with various types of host or control computer systems regardless of their format can be obtained by programming the control computer in the scanner from the host so as to provide the bar code signals which are received by the host and the commands which are generated by the host and transmitted to the scanner in the desired polarity and level and with the desired protocol or format.
With the inventive system hereof, all of the control functions necessary or desirable from the scanner are obtained by way of digital control with a microcomputer which is mounted in the scanner.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other objects, features and advantages of the invention as well as a presently preferred embodiment thereof will become more apparent from a reading of the following description in connection with the accompanying drawings in which:
FIG. 1 is a side view of a bar code scanner and reader system in accordance with the presently preferred embodiment of the invention;
FIG. 2 is an end view from the right of the scanner/reader system shown in FIG. 1;
FIG. 3 is a top view of the scanner/reader system shown in FIGS. 1 and 2;
FIG. 4 is a sectional view of the reader shown in FIGS. 1, 2 and 3, the section being taken along the line 4--4 in FIG. 2;
FIG. 4A is a fragmentary sectional view doing the line 4A--4A in FIG. 4;
FIG. 5 is a sectional view of the scanner shown in FIGS. 1 through 4, the view taken along the line 5--5 in FIG. 4;
FIG. 6 is a fragmentary sectional end view of the scanner shown in FIGS. 1 through 5, the section being taken along the line 6--6 in FIG. 4;
FIG. 7 is a diagramatic view illustrating the performance of the elliptical beam shaping system of the scanner shown in the preceding figures;
FIG. 7A is a plot showing the variation in width and length of the laser spot in the far field and illustrating that the aspect ratio (length/width) remains constant in the far field throughout the scanning range of the system;
FIG. 8 is a sectional view illustrating the laser diode and its optical assembly, the laser diode being mounted on the printed circuit board of the scanner shown in FIGS. 1 through 6 and schematically in FIG. 7;
FIGS. 9 through 11 are diagramatic views illustrating the operation of the optics of the scanner shown in the preceding figures in producing the outgoing laser beam and in receiving the incoming return light scattered from the code;
FIG. 12 is a perspective view illustrating one of the halves of the housing or casing of the scanner illustrated in FIGS. 1 through 6 when viewed from the rear;
FIG. 12A is an enlarged sectional view of the area inside the lines 12A--12A in FIG.12.
FIG. 13 is a prespective view of the housing half shown in FIG. 13 when viewed from the front;
FIG. 13A is an enlarged sectional view of the area inside of the lines 13A--13A in FIG. 13.
FIGS. 14 and 14B are block diagrams of the electronic system of the scanner/reader illustrated in the preceding figures;
FIG. 14A is a schematic diagram of another embodiment of the motor control circuit of the system shown in FIG. 14;
FIG. 15 is a flow chart illustrating the overall programming of the digital computer (microprocessor) of the system shown in FIG. 14;
FIG. 16 is a flow chart illustrating the program utilized in calibration of the automatic gain control codes (CALAGC) of the program shown in FIG. 15;
FIG. 17 is a flow chart of the automatic gain control program of the digital controller;
FIG. 18 is a flow chart of the motor control program (the SCAN BEAM routine) of the program illustrated in FIG. 15;
FIG. 19 is a flow chart of the routine for generating the scan control signals to the scanning motor which is carried on during the scan beam routine; and
FIGS. 20 and 21 are tables of values which are stored in the computer and used in the program illustrated in FIG. 19 for generating the pulse width modulated motor drive pulses.
DETAILED DESCRIPTION
Referring first to FIGS. 1, 2 and 3, there is shown a hand held scanner/reader for bar code symbols. A housing 10 contains the electronics and optics of the unit. It is a bi-part housing having right and left halves 12 and 14 which are assembled together along a parting plane 16 where the halves interconnect. The housing has a head portion 18 and a handle portion 20. The front of the head portion has an opening in which a window 22 of transparent material is disposed. The scanning beam is projected out of this window towards the bar code and light scattered by the code is returned to the window to be detected and processed by the optical and electrical components within the housing 10.
The head portion 18 has an indentation 42 for a label. Another indentation 44 in the handle can also receive a label.
The front of the head portion 18 also carries feet 24 of elastomeric (rubber) material which provides a rest for the scanner/reader unit on the feet 24 and at a point at the end of the handle 20 where an end cap 26 is attached. The end cap is a cup shaped member having an opening 28 through which a detent catch 30 extends to latch the end cap on the end of the handle 20. An electrical cable 32 protected by a grommet 34 which may be part of a strain relief for a male part of a modular connector 36 contained within the grommet which connects the wires in the cable 32 to the female part of the modular connector 36 (see FIG. 4) in the end of the handle. The modular connector may be released by inserting a pin through an opening 38. Another opening 40 provides access for a chain or rope from which the unit may be hung for ready access by the operator.
The rear end of the head portion is adapted to receive, in an indentation 46 therein having holes 48 in which catches are formed (see FIG. 12), a block or strip 58 with openings through which indicator lamps 60 and 62 extend. These lamps extend through a slot 64 in the rear end of the head 18 (see FIG. 12). The lamps 60 and 62 may be light emitting diodes (LEDs) which indicate that scanning is going on by being illuminated in one color (e.g., amber) while the other LED 62 may be of another color (e.g., green) to indicate that a bar code symbol has been successfully read. The strip may contain a connector for a display module (for example using a liquid crystal device) which reads the bar code message or other data (for example during self test using self test routines entered on receipt of command codes from the host computer or terminal associated with the scanner) which is generated in the operation of the scanner/reader unit or in the testing thereof. The display module attaches to the scanner via catches that engage holes 48.
The handle portion has a trigger button 66 which is movable into and out of a hole 68 and operates a switch or variable resistor device which can switch the unit on or off and can control the length of the scan so as to aim and position the beam for scanning desired codes; for example, one of several codes which may be printed closely adjacent to each other on the side of a package or a sheet containing bar codes.
Referring to FIGS. 4 through 6, 12, 12A, 13 and 13A, the design of the housing 10 in accordance with the presently preferred embodiment of the invention will become more apparent. The housing halves 12 and 14 are held together by screws 70 which are threaded into posts 72. There are similar posts with holes therethrough in the left housing half 14. The trigger 66 is a bell crank which is journaled on a pin 74 surrounded by a sleeve 76 to form a re-entrant structure which provides a long path and acts as a shield for static electricity from the outside of the unit into the inside of the unit where the electronic circuitry is disposed, thereby protecting that circuitry against adverse affects of static electric discharge. A nose 78 of the bell crank trigger 66 engages a spring biased switch button 80 which biases the button 66 outwardly of the housing to the position shown in FIG. 4. This nose is rigid and has a gusset 79 to insure that there is no flexure thereof. The switch generates a trigger command in the electronics when it is actuated.
Attached either to the inside of the trigger button (as shown) or to the outside surface of the handle which is opposed to the inside surface of the trigger button is a pad 82 of variable resistance material, the resistance of which decreases as a function of the pressure or force applied by the operator when he or she pulls the trigger. A device known as a force sensing resistor obtainable from Interlink Electronics of 1110 Mark Avenue, Carpinteria, Calif. 93013 may be used as the pad 82. The pad has leads 84 which extend to the electronics of the unit. The arrangement is shown in FIGS. 13 and 13A. It will be understood that the use of a variable resistance pad is optional, but desirable when the length of the scan across the code is to be manually variable.
The parts 12 and 14 of the housing are coped at the parting plane 16 to define an overlapping joint best shown in FIG. 12A. This joint provides a long discharge path for static electricity and serves to shield the electronics within the housing.
The front end of the housing has ribs 86 which define a channel for securing the window 22. On the inside surface of the head portion 18 there are provided tracks which define a generally U-shaped channel 88. In the right hand head portion 12 shown in FIGS. 12 and 13, the ends of this channel 88 are spaced inwardly from the parting plane 16. There is a gap 90 (FIG. 12A) between the ends of the channel in the halves 12 and 14 of the housing. In the channel 88, there is disposed a printed circuit board 92 which carries the optical and electronic components of the scanner/reader unit. This board, with the components thereon, are inserted in one of the halves in the channel 88 therein and then, as the housing halves are assembled, into the channel in the other half of the housing. No shock mounts are used to support the board and its opto/electronic assembly. It has been found that this arrangement supports the assembly in a manner to prevent damage from shock loads, for example when the unit is dropped onto the floor.
Ribs 94 extend along the roof of the head portion and serve to deflect ambient light which may enter the head portion through the window 22 away from the light collection components of the electro-optic assembly. Ribs 96 on the sides and top of the head portion and stiffen it against deflection and serve as light baffles. The bottom of the head portion has an internal shelve 98 in which a male multi-pin connector 100 is fixedly disposed (see FIG. 4). This connector is wired to a male part of another connector 102 which is attached to the bottom of the printed circuit board 92 via a ribbon cable 105. The connections from the cable 32 are made via a printed circuit board 104 in the handle. This printed circuit board has the modular connector 36 at the lower end thereof and the female part of the connector 100 at the upper end thereof.
The handle portion 20 has ribs which define channels 106 and 108 on the forward and rear sides of the handle in which the board 104 is inserted. The board 104 has a notch defining an opening 110 in which a battery 112 is contained. The battery 112 has its terminals in contact with spring contacts 114 on the lower edge of the notch part of the board 104. These spring connectors urge the battery out of the housing when the end cap 26 is removed. To retain the board 104, there is a projecting catch 116 which latches either in a notch in the edge of the board 104 as shown or under the board 104. The modular connector 36 is attached to the lower end of the board 104 and engages a male prong which extends from the cable 32, the male part of the modular connector being formed in and extending inwardly of the housing through the end cap 26.
Another channel for another printed circuit board is provided by a rib 116 in the handle portion 20 of the housing part 12 and an opposed rib (not shown) in the other housing part 14. Another circuit board 120 containing other, optional circuits of the scanner/reader unit forms an assembly with the board 104 when connected thereto via a bridging connector 122 (see FIG. 4A). Then both boards 104 and 120 are desirably inserted at the same time into the assembled housing when the end cap 26 is removed.
The housing parts are preferably made of plastic material, such as polycarbonate or ABS. A groove 124 in which a elastomeric seal 126 may be located seals the open end of the handle 20. The sides of the handle 20 are formed with grooves 127 (see FIGS. 12 and 13) which renders the lower end of the handle flexible so that a boss can flex outwardly through the hole 28 and act as a detent catch to hold the end cap 26 in place, with contact made in the modular connector 36 and with the battery 112 held in place.
The optical and electrical assembly on the printed circuit board 92 has as its major components, in addition to the board 92, a collection mirror 128, a laser diode assembly 130, a photodetector and scanning motor assembly 132, and a beam deflector in the form of an oscillating or dithering mirror 134. A flexible printed circuit board 136 is connected to the board 92 and extends upwardly behind a holding member 138 (FIGS. 12 and 13). The flexible board 136 carries on one leg 136A or a pair of legs 136A & B, the LEDs 60 and 62, and a connector (not shown) which extends through the slot 64 for connection of the LCD display (if such a display is used). The flexible board 136 is folded much like a ribbon inwardly of the board and then outwardly. The leg 136B have wiring which is connected to the laser diode in the laser diode assembly 130 and the motor in the photodetector motor assembly 132.
The mirror 128 has a spherical reflecting surface 138 which faces the photo diode 140 in the assembly 132. This mirror 128 has a base 142 with a flexible tab 144 and side flanges 146 which form rabbett joints with the side edges of the board 92. These edges are coped inwardly so as to provide clearance for the flanges 146. The tab 144 is flexural and acts as a detent latch which latches in an indentation 150 in the board. The positioning of the mirror is not critical because the outgoing and return beam extend over conjugate paths so that positioning errors are automatically compensated. The center of the mirror has a planar facet 152 which deflects the beam from the laser diode to the mirror 134. The mirror receives the scattered light returned from the code as the oscillating mirror 134 scans, collects that light and directs it to the photo diode 140.
The motor assembly 132 includes a motor 160 having a shaft 162. The mirror 134 has a rear bracket 164 with a vertical slot 166 so as to enable the mirror, which may be plastic material, to be force-fit onto the shaft 162. The motor 160 and the photo diode 140 are assembled by a cover 168 which has flanges 170 which are rivetted or screwed to the board 92.
The laser diode assembly 130 is shown in greater detail in FIG. 8. It includes a barrel 174 which is attached as by screws to the board 92. A laser diode 176 is positioned in the rear end of the barrel 174. A lens assembly 178, including a gradient index lens 180, is screwed into the barrel 174. The orientation of the laser is such that the long dimension of the laser beam is generally parallel to the plane of the board 92 thereby utilizing diffraction for orientating and shaping the beam which is incident on the code, as described in detail below.
Other circuit components, including a microprocessor chip, which are discussed in greater detail hereinafter in connection with FIG. 14, are mounted on the board 92. They are not shown in FIGS. 4, 5 and 6 in order to simplify the illustration.
Referring next to FIGS. 9, 10 and 11, there is shown the arrangement of the optical elements which has the feature of eliminating parallax induced errors in the detected bar code signals while allowing all of the optical elements to be arranged on the single printed circuit board 92. The laser assembly 130 projects a beam along a first path 180 to the facet 152. The facet is tilted upwardly so as to project the beam along a second path 182 to the mirror 134. The mirror is tilted slightly downwardly and projects the outgoing beam along a path 184 through the window 22 towards the code to be recognized. In FIG. 10, the outgoing beam is shown by the relatively thin line made up of long and short dashes while the incoming or return light is shown by the heavier lines of long and short dashes.
The mirror 134 oscillates back and forth about the center of scan (a line between the end points of the scan). Preferably, the center of scan extends through the center of the window 22. The scan angle may, for example, be plus or minus 15 degrees about the center of scan as shown in FIG. 11. This scan angle is sufficient to scan the beam across codes within the scanning range of the unit. This range may start at the window or at a distance exterior from the window 22 depending on the anticipated location of the codes to be read. The scanning range is determined by the diffraction beam forming process as will be explained hereinafter in connection with FIGS. 7 and 7A. As the outgoing beam scans, its long dimension remains in a plane approximately parallel to the plane of the board 92. This plane may also be parallel to the plane of the top of the housing head portion 18.
The return light is scattered and fills the mirror 134. The mirror deflects the return light downwardly along a path within the lines 186A and B. It will be noted that this return path 186, when in the center of scan, is in the same plane as the path 182 of the light which is projected out of the scanner unit. The return light is then collected by the mirror 128 and focused, because of the spherical curvature of the mirror, at the photodetector 140.
Parallax is eliminated because there is symmetry between the outgoing beam and the beam of return light. This symmetrical arrangement of the beams is provided because of the use of the facet 152 in the center and along the optical axis of the collection mirror 128. As viewed with respect to the collection mirror, the distance of the outgoing beam to the code and back from the code is the same (i.e., the code is symmetrical relationship with respect to the collection mirror). The light executes the same path going out and coming in from the code. Therefore, symmetry is preserved even though the laser diode is offset from the photodetector and the beam from the diode makes an acute angle to the plane in which the paths 182 and 184 are contained. Accordingly, all of the optical elements can be placed conveniently on the printed circuit board and mounted thereon without introducing parallax caused errors which can adversely affect the uniformity of intensity of the light collected from the bar code over the scan light.
The design of the optics provides a elliptically shaped beam throughout the range in which the code can be located during scanning to derive the bar code signal. This elliptical shape is upright; the major axis of the ellipse being along the bars and spaces of the code. As compared to scanning with a beam which forms a circular spot, the elliptical beam is preferable because of the averaging effect over defects and deficiencies in the code. The aspect ratio of the ellipse is selected to provide adequate averaging of the code and relative insensitivity to scan line tilt. An aspect ratio of the ellipse can be chosen so that there is no apparent difference between an elliptical scanner or a circular scanner with respect to scan line tilt. An aspect ratio of five (5) to one (1) is suitable to accomodate a scan line tilt of 15° at the extremes of the scanner's working range.
The operating range of laser based bar code scanners which have been designed in accordance with traditional geometric optics have utilized large F number elements in order to achieve a desired scanner range, because the scanning range is determined by the depth of focus. To maintain a beam in an elliptical shape, traditional geometric optics resorted to apertures and focusing lenses for beam shaping. Traditionally a elliptical beam was formed using a lens system to collimate the beam from the laser. The collimated wavefront was transmitted through the oblong or rectangular aperture and then focused with a lens so that the narrow dimension or waist of the beam remains of substantially constant diameter over the operating range of the scanner. The operating range was restricted by the F number of the outgoing beam. It was further restricted because of the 90 degree flip of an elliptical beam formed by an oblong aperture. After the position in space at which the beam flips the beam is disposed with its long axis transverse to the code, diminishing severely the resolving power of the scanner. This invention utilizes diffraction effects to provide the beam with the desired profile (oblong or elliptical) and with the desired orientation (major or long axis in the direction of the bars and spaces of the code) throughout the desired working range of the scanner.
Consider the full width, half maximum spot size of a beam transmitted through an aperture. The size is determined by diffraction effects. FIG. 7A considers the beam in two parts. One, the long part of the beam (along the major axis or the height of the ellipse). The other curve in FIG. 7A illustrates the resolving axis and considers its length which is along the minor axis of the ellipse. In both cases, near field diffraction first occurs. This is also known as Fresnel diffraction. The beam size decreases, for example, to about one-third to one-fourth of its size at the aperture (exit pupil of the light source). The minimum spot size depends upon the aperture size and occurs approximately at the Fresnel distance from the exit pupil of the source. This distance is equal to the square of the effective aperture size divided by the wavelength of the light (this is essentially monochromatic light when a laser, such as a laser diode is used). When the Fresnel distance is passed, an elliptical beam flips its orientation. This is shown in FIG. 7A by the relationship of the spot size along the ellipse height and the resolving axis of the ellipse.
The near field region terminates at the Fresnel distance. The longest Fresnel distance is defined by the length or ellipse major axis at the effective aperture. Beyond this point the region of far field diffraction (sometimes called Fraunhofer diffraction) exists. In the far field region the spot size increases. The increase is, however, approximately proportional to the reciprocal of the aperture size (1/aperture size). FIG. 7 illustrates the profile of the spot in four planes, each displaced further from the scanner, but all within the range in which far field diffraction occurs. The inversely proportional relationship of the aperture size along the resolving axis and along the ellipse height is used to advantage in order to make the aspect ratio (ellipse height/resolving axis length) constant throughout the far field range. The substantially constant aspect ratio is apparent from FIG. 7A. FIG. 7A also shows that the slope of the spot size variation with respect to distance from the source is such that the slope of the spot size variation in the far field is proportional to the reciprocal of the aperture size.
The shortest Fresnel distance (determined by the largest aperture dimension--in this case, the ellipse height) is often desirably within or near the scanner housing or inside or near the window 22 of the scanner shown in the preceding figures. In order to locate the far field diffraction range starting a few inches away from the window 22 and also to provide a phantom aperture which will maintain the aspect ratio of the elliptical beam in this scanning (far field diffraction) range using the diverging beam from a visible laser diode, it is desirable to use a very short focal length lens. The effective Fresnel distance D eff ) with a lens is reduced as a function of the focal length of the lens in accordance with the following relationship:
1/D.sub.eff =1/D-1/f
Where D is the Fresnel distance as determined by the aperture size and the wavelength of the light and f is the focal length of the lens. A gradient index lens 180 is preferably used as a short focal length (for example 2.5 mm focal length lens). The effective aperture is formed where the lens begins to focus the diverging wavefront from the laser 176. This is called the principal plane of the lens and is effectively the exit pupil of the source where a phantom aperture exists. Locating the lens principal plane with respect to the laser 176 also determines the phantom aperture plane location and, the size of the ellipse and the resolving or minor axis of the ellipse. As shown in FIG. 7, the ellipse height at the principal plane (the phantom aperture) is desirably disposed transverse to the code so as to take advantage of the flip in the profile which occurs after the longest Fresnel distance. Accordingly, the beam forming diffractive optics of the invention, makes advantageous use of far field diffraction and simplifies the optics by elimination of apertures and needs only a single lens to set the size of a phantom aperture.
Referring next to FIG. 14, there is shown the electronic circuitry of the bar code scanner/reader. All of this circuitry may be located on the printed circuit board contained in the head of the unit. The printed circuit board also mounts the collection mirror and the deflector (scanning mirror) and its motor. The feature of the electronic system shown in FIG. 14 is that it is totally digitally controlled. Some of the principal parts of the circuitry are: (a) the front end or bar code reading circuits 140; (b) the laser regulating and drive circuits 144 which control current to and drive the laser diode LD and photo diode PD assembly 142; (c) motor drive circuits 146 which operate the motor 148 which is a stepper motor having phase A and B stator drive coils; and (d) interface circuits 150a and 150b which output the bar code signal and receive command signals and data from the host computer. There are also indicator (display) circuits 152 which include LEDs.
Digital control is provided by a computer system 154 having a microprocessor 156. An analog to digital converter (ADC) 158 and a nonvolatile memory (NVM) which may be an electrically erasable programmable read only memory (EEPROM) 160 are associated with the microprocessor 156. The microprocessor may be a commercially available chip such as the Motorola MC68HC705C8. This chip has a multiplicity of ports DP0 to DP21 which may be used to receive data and commands and to output data and commands. The microprocessor may be programmed from the host computer with data which arrives on the ACK line through the interface logic 162. Under programmed control, an output command SDPOL is provided by the state of the SDPOL line from DP3 to make the scanner compatible with the polarity and level of the data from the host computer. Universal compatibility with various types of hosts is, therefore, provided. This data is outputted on the serial data input (SDIN) line to DP2 of the microprocessor 156 and thence delivered on the data input line (DI) from port DPI to the memory 160 where the program is stored. The memory is enabled to receive programming data by clock signals from the computer chip 156, when an enabling line CS1 of 4 enabling lines which selectively enable the various peripherals (the ADC 158, the NVM 160 and the digital control elements in the front end 140 and in the regulator 144). In this way, the various peripherals can be multiplexed for input and output of data to the microprocessor 156.
The scanner is enabled either by the trigger switch (TRIG-SW) in the scanner or from the host in response to an enable command. The application of power may also enable the scanner. Thus, the scanner can be enabled three ways either with the trigger switch, the enable input, or by application of power. The scanner could be enabled by any scanner input by suitable modification of the program. The interface 150a has logic 164 which handles these enable signals and ORs them to generate a WAKE signal which operates the power control 165 as by setting a flip-flop (F/F) which then turns on a voltage regulator circuit 166. The circuit 166 has a regulator chip of conventional design which regulates the output supply voltage from the computer, power supply, portable terminal or battery in the handle of the scanner and provides a regulated voltage indicated at +V, which may be 5 volts. The power stays on until a SLEEP command from port DP9 of the microprocessor 156 is generated, either on code detection or after a time-out, as may be programmed by the programming data in the memory 160. This operation conserves battery power to increase battery life.
The programming data is stored in the memory 160 under control of the microprocessor 156. It may be desirable to read the programming data. Then, that data is made available on the SD out line from the port DP4 of the processor 156. The output data (serial data output) is multiplexed under program control in the microprocessor 156 and supplied to an output line (BCV bar code video or PROG.DATA) from the interface logic 150b. The polarity of the output data, whether BCV or program data is controlled by the BCPOL line to be compatible with the host computer.
The host computer operates to decode the BCV signal. The BCV signal is obtained from the front end 140 and represents the bar code message by the analog timing of the pulses thereof. The host may use conventional decode logic to obtain the bar code message which is received. Another output from the interface logic 150b is the start of scan (SOS) signal which indicates when the beam is at the starting ends of its scan, either on the right hand or the left or both. The program in the microprocessor which controls the scanning motor 158 to oscillate the mirror provides the SOS output which is a level which changes state at the end of scan. This is to be distinguished from the BCV or program data level which is controlled by BCPOL depending upon the requirements of the host. The bar code video may be black high or white high. The scanner generates BCV as white high in this embodiment of the invention, which can be converted to black high in order to meet the requirements of the decoder in the system computer with which this scanner and other scanners in the system work.
The front end 140 has a photo diode circuit 168 which develops a current signal depending upon the intensity of the return light. This signal is converted into a voltage signal by a transimpedence (TRANS-Z) amplifier 170. The voltage signal is then differentiated in a differentiating circuit 172 to follow the transitions in the signal which correspond to the locations of the edges of the bars and spaces. A digital control element 174 in the form of a digital potentiometer provides forward gain control to the first amplifier in a chain of amplifiers 176 and variability of translation of the return light into signals which represent the bar code. The gain control is automatic and the digital pot 174 is set by the digital input (DI) which is stored in a register in the digital pot 174 when it is enabled by the enabling signal CS2. The digital pot 174 may be 1/2 of a dual pot circuit element containing another digital pot 178 which is used as the digital control element in the laser regulator circuit 144 and will be described hereinafter. The DI signal may be, for example, 16 bits stored in a common register of the dual pot 174 and 178, the pots using the first and last 8 bits in the register (DP1 and DP2).
The gain of the front end is set under computer control. Since the scanner scans in opposite directions and the velocity of scan or intensity of the return light may be different in each direction of scan, the digital pot 174 is set to follow the intensity of the return light not on the immediately preceding scan but the scan which occurred before the immediately preceding scan or on alternate scans. The program then changes the gain on alternate scans so that the amplifier output signal amplitude stays constant from scan to scan. In addition the relationship between the intensity of the return light and the gain (the sensitivity of translation of the returb light into electrical signals which provide the BCV) may be in any desired functional relationship, whether linear or non-linear, under program control which sets up the relationship between the value of DI and the signal corresponding to the intensity of the light.
It is desirable to turn off the front end so that spurious illumination does not generate signals which may be confused with actual bar code video output or program data. To this end the microprocessor generates a not-kill bar code (KBC) which enables the amplifiers to transmit output signals only during actual scanning operations. The signal which controls the gain in accordance with the intensity of the return light is a peak detector circuit 180 which follows the peaks of the gain, and therefore the sensitivity of translation, controlled differentiated voltage representing the bar code. The output of the circuit 180 is a voltage level DPD. This level is digitized in the ADC 158. The ADC has a plurality of channels one of which (CH1) receives DPD. Analog to digital conversion is enabled when the chip select CSO is high and also when a code (DI) from the microprocessor identifying the channel to be digitized exists.
The voltage representing the bar code is translated into analog pulses (the BCV) by a discriminator circuit 182 including a comparator 184 which compares the differentiated signal with a peak voltage on a capacitor 186 charged through oppositely polarized diodes 188. The design of the discriminator 182 is the subject matter of U.S. patent application Ser. No. 832,878, filed Feb. 10, 1992 which is a continuation of application Ser. No. 518,608, filed May 3, 1990 in the name of Jay M. Eastman and assigned to the same assignee as this application, now U.S. Pat. No. 5,210,237, issued May 11, 1993. The discriminator outputs BCV which is applied to a port DP7 of the microprocessor 156 and also may be applied to the host computer via the interface logic 150b.
The laser regulator circuit includes a control loop having a comparator 190 which outputs an error signal to a driver amplifier 192 thereby controlling the current through the laser diode LD. This current is available at ILS and is applied to CH0 of the ADC 158 for digitization during laser output power regulation and also during initialization of the laser to set its power output. The control loop includes a photo diode PD which is optically coupled to the laser diode and provides an output current across a resistor 194, representing the laser optical output power, which is compared with a reference signal input to the comparator 190 to derive the error control signal for controlling the laser current. This reference signal is obtained from the digital pot 178 which receives a regulated reference voltage at one end thereof. In order to prevent the laser from being turned on except during a scan, a transistor switch 196 drives the reference signal input to the comparator 190 to ground thereby cutting off current to the laser diode.
The optical power is calibrated to a desired power which is represented by digital signals in the memory 160 by setting the digital pot 178. During calibration, in manufacture of the scanner, an ILS value corresponding to the desired optical power as measured by an exterior power meter is obtained and the corresponding ILS value stored as a parameter in the memory 160 or elsewhere in the microprocessor 156. Then the digital pot resistance is changed to increase the reference voltage applied to the comparator 190. During normal scanning, if ILS exceeds predetermined current value (e.g., 25% above nominal operating current as might be the case if the laser is operated at a temperature over its recommended maximum operating temperature), the laser is turned off. Then, operating the trigger switch or receiving an enable from the host computer will not cause the laser to be powered up at an excessive current which might destroy the laser.
During normal laser regulating operation, the value of the reference voltage as obtained across the digital pot 178 stays constant and the control loop regulates the laser current in order to maintain ILS at a desired value for prescribed laser optical power output.
During factory calibration, the digital pot 178 setting is determined upon command of the external computer and optical power meter, whose analog output is attached to the ADC's 158 PWCAL input through a buffer amplifier 159. The calibration procedure is controlled by the scanner's microprocessor in the following manner. The digital pot setting is steadily increased from minimum to maximum power while both the laser current (ILS) and optical power PWCAL are monitored. When the measured power agrees with the requested power (sent by the external computer as part of the command), the scanner's microprocessor saves the digital pot setting and laser current readings in NVM 160. If, during calibration, several different pot settings are tried without a difference in measured power being noted or excessive changes in measured laser current are noted, the calibration mode is cancelled (to protect the scanner's circuitry) and a "calibration failed message" is sent to the external computer.
The motor windings are driven by current pulses, the direction of which in each coil is controlled by push-pull amplifiers (PPAMPL) 198 and 200 for coil A and 202 and 204 for coil B. These pulses are controlled in duration by the duration of the motor control levels SDAA1 through SDBA2 from the microprocessor 156. In other words, pulse width modulation is used to produce waveforms on the coils A and B to control the motor to provide generally linear scan velocity. Moreover, the maximum pulse width determines the length of the scan. In prior motor controls systems, bias current was applied to one winding, while the current to the other winding was changed linearly. Such linear change does not produce a linear velocity during the scan. By pulse width modulation control (microstepping), the requisite non-linear variation in current to the. coils during the scan can be obtained to obtain a generally linear sweep velocity over the scan. By controlling the direction of the current, the motor and the oscillating mirror can be centered so that the center of scan is approximately at the center of the window thereby avoiding the need for mechanical centering.
The scan length (scan angle) is controlled by controlling the amplitude of the average current in each coil during the scan. The higher the average current through the coil the larger the excursion. Thus by increasing the duty cycle over the scan, the scan angle increases.
Control of scan length is obtained using the microprocessor 156 and an analog triggering mechanism represented as a resistor 206 having a resistance which is inversely proportional to the force or pressure applied by the trigger thereon. This resistor may be a pad of polymer material which is commercially available and called a force sensing resistor (effectively a strain gauge). Such pads are obtainable from Interlink Electronics of Santa Barbara, Calif. 93103. The voltage across the variable resistor pad 206 is presented to channel 2 of the ADC 158. Under program control, the microprocessor in response to the digital input (DO to DP0), the average current is changed in response to the pressure applied by the operator against the trigger and thence to the resistive pad. At the beginning of a scanning operation, very little force can be applied thereby providing a very narrow scan suitable for aiming the beam at a particular code, which may be one of a multiplicity of closely spaced codes on the side of a package or a sheet of paper. The spot where the beam is incident is bright because the beam is not spread out thereby facilitating aiming. Once the code is located, the pressure can be increased and the scan length (scan angle) increased in accordance with the microprocessor's program which varies the timing of the output levels SDAA1 through SDBA2 on DP10 through DP17.
The microprocessor also provides outputs SLED and GRLED which may be low during scanning and following the successful reading of a bar code symbol and when the power control is on (between the times of occurrence of the wake and sleep commands). Then the SLED or the GRLED 152 will be lit.
It has been found that a simplified motor control circuit such as shown in FIG. 14A may be used in which only two commands SDAA1 and SDBA1 are needed. Then current flows through the motor coils A and B only in one direction. It has been found that by modulating the duty cycle of the SDAA1 and SDBA1 pulses which are applied through RC damping circuits, the scan velocity and length may be controlled. The scan oscillation or repetition rate is also controlled by the periods during which the motor control pulses execute a cycle (i.e., the maximum duty cycle or period of the pulses). The programming of the microprocessor 156 to obtain the digital control functions discussed above, will become more apparent from FIGS. 15 through 19.
The overall program is called Power On Start. The CPU is first initialized. New data is loaded into the microprocessor internal memory from the external non-volatile memory (NVM). This is done every time a wake signal occurs; the wake signal acting as an interrupt to go to the initialize process.
The next process is the calibration of the AGC which determines the amplifier's bias voltage by averaging many samples of DPD under no signal conditions (laser off and motor stationary). This process compensates for scanner-to-scanner component tolerance variations.
The CAL AGC routine is shown in FIG. 16. The digital pot in the front end is reset to its maximum resistance. Then, 256 samples of DPD are read via the ADC. The reading is accomplished at the maximum clock rate of the ADC.
The 256 samples of DPD are averaged. The average is named CAL. This average is used in computing the digital control signal to the digital pot 174 to set the amplifier gain during scanning operations. The program is described hereinafter in connection with FIG. 17.
Returning to FIG. 15, the program next sets the time delay for the generation of a sleep command after occurrence of a wake command. Then, all of the interface functions are set up utilizing the program data. At this time, if the host computer desires, the program can be checked by reading out the stored program back into the host. Levels corresponding to data states (polarity) and formats are now set up in the system and the system is now capable of receiving new commands. The decision is whether a command arrived on the ACK, EN (enable) or TRIG (trigger) or any combination thereof. If so, the system jumps to the routine called motor (MTR) which generates the pulses for operating the scan motor to scan the beam. During the scan routine, the laser power is regulated as will become more apparent from FIG. 18.
The system then waits for a decision as to whether either a sleep command was generated or if external serial data from the host computer contained another command. This other command may be a new program, a command to calibrate the laser diode so as to set a safe level of optical output power as required by governmental regulations or the like. A sleep command can also be generated by external data, for example, that a bar code has been decoded. After the sleep command occurs, the power to the laser diode is shut off and the system stays idle until the next wake command.
FIG. 17 illustrates the AGC routine. First, the CHI of the ADC is enabled to read the DPD level. Next, during scanning, the CPU reads DPD via the ADC approximately 100 times and stores the 16 largest readings at the frame's end. The average of these 16 values is used as DPD in the equation shown in FIG. 17. Gain codes (digital control signals) corresponding to G' are generated on each scan. Gain codes are used to control the gain for scans in the same direction as the scans on which they are derived. Therefore, two values of G' for alternate scans are stored. These are shown as LG' and RG' for scans to the left and to the right, respectively. The program controls the microprocessor to apply these alternate values to the DI data line to enable the digital pot 178 to control the gain in accordance with LG' and RG' values on alternate scans.
Referring to FIG. 18, there is shown the MTR routine during which the beam is scanned across the code. The routine starts by initializing values. The scan LED (SLED) is set high so that that LED is lit. The bar code polarity (BCPOL) is set so that the host computer and its decoder will receive bar code white high or black high levels corresponding to the bars and spaces of the code as required by the decoding format. Next, not kill bar code (KBC) is cleared, thereby allowing the amplifier chain 176 (see FIG. 14) to pass the differentiated bar code signal to the discriminator 182. The digital pots are set to their calibrated values both in the regulator (DIGPOT 178) and the AGC control in the front end 140 (DIGPOT 174). In order to initialize the routine which generates the scan motor drive pulses, a code representing the off period (OFFPER) for each scan current pulse cycle is then set to 0 value.
In order to understand the meaning of OFFPER and, in general, how the scan motor drive pulses are generated, consider FIGS. 20 and 21. These figures show the pulse width table and the SD (port) signal values. The tables are stored in memory (in the NVM160--FIG. 14). The pulse width table stores N pulse width values, 16 of which represent the motor coil current durations during a scan in one direction (e.g., to the left) and the remaining 16 (total 32) represent the durations of the current pulses for the scans in the opposite direction (to the right). In effect, the table represents the waveforms of the motor drive current during each scan in terms of corresponding pulse width modulated signals. It will be appreciated that a single pulse does not produce an entire scan but a series of pulses (in this case, 16 for each scan direction--8 for each phase) of different duty cycle define the waveform which controls the motor to execute a scan. The maximum duty cycle may for example, correspond to 16 clock pulse periods; the periods occurring at a rate of 240 per second (divided down from the 1 MHz microprocessor clock). The maximum period of the current pulse corresponding to 50% duty cycle is then 16 clock pulse periods. This maximum period is denoted by the symbol A in the flow chart for the scanning routine shown in FIG. 19. The off period is the difference, i.e., the maximum duty cycle period A minus the period of the pulse, t i . In the pulse width table, the t i pulses have values from 0 to 15 which is the number of clock pulse periods per maximum duty cycle. It will be noted that the entire duty cycle is preferably not used. Thus, the pulse width table may store 32 (N=32) values which vary from 0 to 15 in numerical value.
The SD (port) signal values in the table shown in FIG. 21 represent the polarity of the current (the current direction) through the A and B coils of the scan motor corresponding to each successive t i value in the pulse width table. Thus, there are 16 index or I values for each scan, I=1; I=2; I=3 . . . I=N. These index values correspond to the pulse width table values, t i =1; t i =2; t i =3 . . . t i =(N+1). N=32 in this embodiment covering a left followed by a right scan. There are therefore corresponding port signal values for each pulse width value. The port signal values are those that exist during the time that the pulse is on, and not during the off period. During the off period the signal values at the ports are all 0 so that no current flows through the motor coils. The current to the phase A coils are controlled by four bits; SDAA1, SDAA2, SDAB1 and SDAB2 as shown in FIG. 14, since these coils are connected through push-pull amplifiers. Similarly, the phase B coil's current is determined by the levels of the ports SDBB1, SDBB2, SDBA1 and SDBA2. Different ones of these ports are high or low or off so as to drive the A coils with current in one direction (A+, or in the opposite direction, A-). Similarly, the phase B ports are either high or low to provide phase B current in opposite directions. In this embodiment only one coil (A or B) receives a pulse during any one of the 16 cycles where a drive pulse can be passed through a motor coil. This conserves battery power. Accordingly, by controlling the port signal values, currents corresponding to the pulse width values in the pulse width table are generated so as to drive the scan motor to oscillate back and forth with a different oscillation (scan) length corresponding to pulse widths, because the average current through the coil during each scan depends on the pulse width. For full pulse widths the durations of the pulses may be the maximum duty cycle or 15 clock pulse periods during each period in which a pulse can be generated (the A periods). The length of the A periods determines the number of scans per second. For 30 scans per second the clock pulses which make up the A periods run at 240 periods per second rate. The rate is increased for a faster scan rate and decreased for a slower scan rate. 30 scans per second is presently the preferred scan rate. The relationship between pulse rate and scan rate can be expressed mathematically as follows: ##EQU1## where, M=Waveform samples/Phase.
In the event that the simplified motor drive circuit of FIG. 14A is used. The motor currents are either in one direction or off. Then, only two SD port signals are used. It will be noted that the last process in the routine of FIG. 18 is to pulse the SD ports to center the motor to the COS (center of scan). This is a desirable but not essential process in that the pulse widths and current directions in the motor coils may be adjusted so as to cause the beam to be centered approximately in the center of scan (which falls midway across the width of the window 22 in the scanner). The table values are obtained experimentally on an interactive basis with the host computer so as to obtain a generally constant velocity over the scan and in the plane of the code being scanned as may be observed by the intensity of the spot as it scans across a plane where the code may be located. To obtain different scan angles, a plurality of pulse width tables may be stored and the table corresponding to the desired scan angle selected.
Returning to FIG. 18, after initialization the laser diode is turned on. A command LDEN is set low, thereby disconnecting the transistor switch 196 from ground and allowing the laser to operate at the level set by the value of the digital signal which controls the digital pot 178 in the laser regulator 144.
Next, the table index is set at 0. A timer is then set to generate the first interrupt which allows entry into the scan routine shown in FIG. 19. This scan routine occurs asynchronously in the program. During the routine there are successive interrupts generated which cause the index to step and thereby output different pulse width table values and cause different corresponding SD port signal values to be generated at the SD ports of the microprocessor 156.
The next step in the routine is to determine if the laser current has exceeded its safe limits. This is done in the microprocessor 156 in response to the laser current value which is digitized in the ADC 158. In the event that the current limit is exceeded, destructive failure of the laser diode could occur. Then, the LDEN command is set high, thereby shutting off the laser diode. As part of this safety aspect of the motor routine, the computer flashes the SLED and GRLED commands on and off so that the operator can realize that the laser has overheated. The operator can then wait until the laser cools down before reattempting to start the system. For example, by pulling the trigger.
If a stop scanning command has been received, the laser diode and the scan LED are cut off. The counter which generates the interrupts in the scan motor drive routine shown in FIG. 19 is then inhibited so that the motor can no longer scan. Then, the operation noted above as being optional to center the motor electronically to the center of scan by pulsing the SD ports is carried out. The motor stops at the center of scan. If desired, the motor can be stopped at the center or at either end of the scan by detecting the table (FIG. 20) index value for the desired stop location and interrupting the motor drive current when that index value is detected. Starting scanning at an end of scan (with the mirror off center of scan), can minimize the time required to read a code, since the first scan is then a complete full length scan.
Consider next the routine shown in FIG. 19 where the scan motor pulses are generated. Generally, the routine has two states which occur respectively while the pulses t 1 , t 2 . . . t N are being generated and while these pulses are off (during A-t 1 , A-t 2 , A-t N ) . The value in the first state is t i and the value in the second state is the off period (OFFPER). As noted above, during initialization, OFFPER is set to 0. The first time through the routine, upon occurrence of the first interrupt OFFPER is 0. In one branch of the routine the SD port signals are fetched from the SD table at the index value I=0, which was set in the second process step in the routine after initialization (see FIG. 18). Next, the off period is computed as the maximum duty cycle A minus the pulse width table value for the I index. The index is 0 on the first pass through the routine.
Next, a timer is set at the pulse width from the pulse width table for the index and an interrupt occurs on time-out. When this next interrupt occurs, the decision as to whether off period equals 0 is negative and the program proceeds to the other state. This is the off period time after the first current pulse. Accordingly, current to the motor windings is cut off. This is accomplished by setting SD port signal values for current cut off and no current flows to the coils (phases A and B) of the motor.
Next, a timer is set to the off period value which was computed during the first part of the routine. An interrupt then occurs on time-out. The next interrupt causes the routine to enter its first state so that the next pulses which drive the motor during the scan are generated. The index is also advanced by computing the index value by the modulo N addition shown in the flow chart of FIG. 19. The program proceeds to generate the next current pulse value. By then, in the other state of the routine the memory containing OFFPER is cleared. Accordingly, when the next interrupt occurs upon time-out of the timer which has been set to OFFPER, the routine proceeds along its first branch. It will therefore be seen that the routine switches from state to state (branch to branch) until a complete scan cycle (scan to the left and scan to the right) is executed.
The index number also represents the start of scan on the left and right scan. For example, index number equal to 1 starts the right scan and index number equal to 17 starts the left scan. The start of scan (SOSPORT) is then inverted to set the scan flag to indicate start of scan. This start of scan signal is used in the decoding process and is detected by the host computer via the interface logic 150b. The laser can be interrupted at these start of scan locations, in response to the table index values (see FIG. 20). The laser is then off where the beam velocity is minimal. This conserves electrical power, and reduces laser light output for safety considerations under computer control rather than by optical detection of the mirror position (see U.S. Pat. No. 4,820,911 of Apr. 11, 1989).
Returning to FIG. 18, it will be noted that the AGC digital pot setting adjustment is made when the SOS flag is on and continues to be made during each scan until the stop scanning command is received. The command may come from the host computer or may be the sleep signal generated upon time-out in the microprocessor.
From the foregoing description, it will be apparent that there has been provided an improved bar code scanning and reader system which is digitally controlled for flexibility in operation with various host computers or terminals to which the scanner/reader may be connected. The invention also provides improved optics, operative by diffraction, for forming the scanning beam and for insuring accuracy in reading by eliminating parallax. The invention also provides features of mechanical design to enhance reliability and reduce fabrication costs. Variations and modifications in the herein described system, within the scope of the invention will undoubtedly become apparent to those skilled in the art. Accordingly, the foregoing description should be taken as illustrative and not in a limiting sense.
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A unitary hand-held bar code scanner and reader produces an elliptical beam, oriented with its major axis along the direction of the bars, utilizing optics employing far field diffraction effects to shape the beam and maintain its elliptical aspect (length to width ratio) constant over a distance in front of the scanner were bar codes may be located. The optics eliminates parallax even though the photodetector and light source (preferably a laser diode) are located offset from each other on a board on which the optics are mounted. A housing assembly has channels which mount the board therein without shock absorbing devices. A digital microcomputer controller and peripheral devices regulate the optical power output from the laser diode and prevents catastrophic failure, if the electrical current through the laser diode exceeds safe limits. Digital control of the gain of the electronic circuits which provide the signals from which bar code information can be decoded and for the operation and control of a motor for oscillating a deflector which scans the beam across the code are also provided utilizing the microcomputer. The microcomputer also controls interface circuits to provide compatibility with auxiliary equipment and host computers which generate commands and requires data inputs of various polarity and format.
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BACKGROUND OF THE INVENTION
The invention concerns a textile machine with a fiber band feed apparatus and a guide element for guiding the fiber band and with a band monitor for detection of band breakage.
In the case of stretch (draw-frame) or flyer textile machines, a feed apparatus for fiber bands is known which is designed as a feed rack or feed table.
With the feed apparatus, that is with a feed rack or a feed table, as a rule, the fiber band is removed from an already positioned can and conducted to the textile machine.
The fiber band taken out of the can is removed upwardly in a vertical direction and then turned by a band guide in a generally horizontal direction. On the way to the stretch machine, the fiber band is taken through further band guides and guided horizontally. This corresponds to a feed rack.
In contrast to this, in the case of a feed table, the band directional turn is made by a driven means, that is, the band guide is designed as a pair of rolls, wherein the under roll is driven and the fiber is conveyed between the said pair of rolls. Additional sequential band guides correspond to those of the feed rack, that is, they are not driven.
Since, obviously, a band guide has the duty of guiding a fiber band, its meaning is completely encompassed in the concept "guide element".
Upon the installation of a feed apparatus, the valid principle is to recognize a band break in the area of the feed apparatus even before its entry into the textile machine, and to recognize this as soon as possible. The feed apparatus can also be applied, however, if the fiber band is to be received from a prior, fiber band generating, textile machine. Even in this case, there is to be in the feed apparatus a guide element with an installed band monitor.
As is shown by EP 302 322 A2, a known band guide guides a fiber band in a feed apparatus and, at the same time, detects a break in said band. A band break releases a signal through the band monitor, which signal is then employed to shut down the machine before the entry of the band end occurs. In this case, the band monitor is integrated into the band guide.
In the band guide, the single fiber band is run between two vertically disposed, outer entries to the band guide. The fiber band slides, in this operation, on a guide surface of the band guide. When sliding on this guide surface, the fiber band undergoes no change from the guided direction. The band guide is equipped with a band monitor for the detection of a band break. The band monitor is integrated into the guide surface of this band guide. This requires special manufacture and technologic integration of the band monitor in the band guide. No conventional band monitor is applicable, but a custom made unit is required. Since the sliding fiber band produces a permanent heating on the guide surface, the integrated electronics of the band guide must assure a high degree of temperature control. These related necessities in their totality, lead to the fact that this band guide with the integrated monitor is very expensive.
The placement of a guide element (band guide) and a conventional band monitor did not bring the desired result since the said monitor, during machine operation, registered band breaks where there were none. These erroneous signals interrupts the smooth running of production.
OBJECTS AND MAY OF THE INVENTION
Thus, a principal purpose of the invention is to make available a band monitor without integration into a guide element and at the same time, to avoid false signals from said band monitor. Additional objects and advantages of the invention will be set forth in part in the following description, or may be obvious from the description, or may be learned through practice of the invention.
One means of achieving this purpose is accomplished in accord with the characterized features of the invention wherein a textile machine is provided for processing fiber band with a feed apparatus for fiber band and a guide element for the guiding of a fiber band and with a band monitor for the detection of band breakage. The band monitor (BW, BW1, BW2, BW3) is always placed in the area of the guide element, in particular, one band guide (BF), and another guide element (FE, FE1, FE2, FE3) is located in the area of the band monitor (BW, BW1, BW2, BW3). In one embodiment of the invention, an additional, that is, another, guide element is installed directly following the said band monitor, positioning being relative to the transport direction of the fiber band.
In yet an alternate manner, the other guide element, again in reference to the transport direction of the fiber band, can be installed directly ahead of the band monitor.
The band monitor and/or the other guide element are adjustable as to position in reference to the transport direction of the fiber band. Advantageously, the band monitor and the other guide element are secured on a supporting element in common with the feed apparatus. Thus, the securing structure can be comprised of a support bracket, one leg of which carries the band monitor and parallel thereto a carrier bar is placed which bears the other guide element. This guide element can be designed as a rod or as an open band guide hook.
If the carrier at one end, along its longitudinal axis, is affixed to the support bracket, then the carrier can be turnable to a fixed position about its longitudinal axis. The carrier is adjustable, to the extent that the guide element can easily deflect the fiber band in relation to its transport direction. In this way, the fiber band is diverted in its transport direction from that direction imparted by the band guide.
The mode of installation can be so carried out that the other guide element is connected with the band monitor by a connection means. This connection piece can be pivotable and subject to being fixed in position, relative to an axis. The rod, which is designed as the other guide element, can be principally vertical in respect to the base of the feed apparatus, whereby this rod is adjustable in horizontal direction, at right angles to the fiber band.
Different installation locations of a guide element, especially of a band guide in a feed apparatus, do not limit the invention. The invention causes the running of the fiber band to be substantially smoother in the area of the band monitor. This in turn brings about the result that false signals caused by the fiber band are eliminated.
The band guide and the other guide element form a touching surface for the fiber band. The fiber band moving between the band guide and the other guide element possesses a relatively smooth run so that no false signal can be released by vibration of said fiber band.
One embodiment of the invention is presented in the drawings and is more closely described in the following.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1: the feed frame as a feed apparatus,
FIG. 2: feed element in the transport direction of the fiber band before the band monitor and the support system,
FIG. 3: adjustability of the support structure,
FIG. 4: guide element mounted on the band monitor,
FIG. 5: guide element after the band monitor, relative to the transport direction, and
FIG. 6: guide element in front of the band monitor, relative to the transport direction.
DETAILED DESCRIPTION
Reference will now be made in detail to the presently preferred embodiments of the invention, one or more examples of which are illustrated in the drawings. Each example is provided by way of explanation of the invention, and not meant as a limitation of the invention. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a third embodiment. It is intended that the present invention include such modifications and variations as come within the scope and spirit of the present invention.
FIG. 1 shows a known feed apparatus Z of a textile machine which processes fibers, which is designed as a feed rack. This feed apparatus Z is comprised principally of a longitudinal member L and two or more supports S1 and S2, which carry the longitudinal member L. The vertical supports S1 and S2 can advantageously be built in the manner of a telescope, by which an adjustment of the feed apparatus Z to accommodate cans of varying heights is possible.
The longitudinal member L carries several cross pieces QS1 to QS6. The cross pieces are affixed according to their centers, so that they extend to each side of the longitudinal member L. The number of the cross pieces is dependent upon the maximum number of cans which can be accommodated at the stretch machine.
The band guides BF1, BF2, BF3, BF4, BF5 which are respectively on an end of a cross piece QS1, QS2, QS3, QS4, QS5 are above a can (the can is not shown) and turn the fiber band arising vertically out of the can over into a horizontal direction (parallel to a non-shown base of the feed apparatus). The band guide is matched to a guide element. Beside the band guide are installed, generally, directional elements LE which serve for the horizontal guidance of a fiber band.
The exit of the feed apparatus Z is formed of a so-called rake R, so that the fiber bands, for instance, can be forwarded from there to the intake rolls of a stretch machine.
These intake rolls are designed as electrical contact rolls, that means that the lack of a fiber band releases an electrical output by the contact roll, so that a signal is given to a control system. Stopping the machine and/or instigating the feed of a backup reserve fiber band are possible reactions which can be generated by the said control system.
FIG. 2 shows a guide element, in particular a band guide BF affixed on a cross piece QS connected to a support structure H, which further carries a band monitor BW (with sensor surface SF) and another guide element FE. The support structure H can be extended as a support bracket HB. The support bracket HB has a leg SL. The band monitor BW is placed on this leg SL. The active sensor surface SF of the band monitor BW is so positioned, that it is set at right angles to the running direction of the fiber band. The support bracket HB also holds a carrier T at a spatial interval from the leg SL. At the end of the carrier T, an intermediate piece ZS is placed at an angle and bears on its end a guide element FE. The longitudinal axis of the guide element FE is arranged perpendicularly to the transport direction of the fiber band.
This positioning of the guide element FE achieves the damping of the vibrating fiber band. The support structure H is so disposed on the cross piece QS, that it is adjustable in the direction (v) on the longitudinal axis of the cross piece QS. Dependent upon the thickness of the fiber band and the characteristics of the material of the fiber band, this permits the band monitor BW to be brought into the exact supervisory position opposite to the fiber band.
This feature is especially important upon batch changes, that is, when the fiber band material or thicknesses are changed. An adjustment means is also provided for the guide element FE (see FIG. 3). The carrier T, which is part of this, can be installed angularly rotatable about its longitudinal axis (direction d) in the support bracket.
A rotation about the said longitudinal axis of the carrier T results in a pivoting of the guide element FE into the transport path TR of the fiber band FB or a retractive pivoting of the guide element FE out of the transport path TR of the fiber band FB. The arrow at the reference TR reflects the direction of transport of the fiber band. Depending upon different materials and thicknesses of various fiber bands, in the course of batch changes the guide element FE can be brought into position at the fiber band. The position in relation to the fiber band FB may be said to have been reached when the guide element FE lightly touches the said fiber band FE. By means of the touching of the guide element FE on the fiber band FB, the effect is created that the vibration, i.e. oscillation, of the fiber band FB is damped and the fiber band FB has a relatively smooth run immediately before the active sensor surface SF of the band monitor BW. The force of pressing of the guide element FE against the fiber band is adjustable by means of carrier T, depending upon the fiber band material currently in use. No delay of the fiber band is allowed to occur.
FIG. 3 shows an arrangement such as in FIG. 2, wherein the transport direction arrow TR of the fiber band is sketched in. If, based on spatial grounds, no adjustment of the support structure H in the direction v is practical, then alternately an adjustment of the band monitor BW in the direction u is possible (FIG. 3). At the same time, the offset of the band monitor BW in relation to the fiber band may be adjusted.
FIG. 4 shows an arrangement of a band monitor BW1 with a guide element FE1, which, by means of the connection piece VM is attached to said band monitor BW1. The guide element FE1 is, in this case, pivotable about an axis A, as is the connection piece VM. Both may now be turned through a circular arc and arrested at a desired position. Band monitor BW1 and guide element FE1 are thus slidable in relation to the fiber band by the corresponding sliding of the support bracket HB1. This movement is possible in the directions v.
The guide element can be designed not only as a rod or a tube, but also as an open hook band guide.
Another embodiment variant is shown in FIG. 5. In this case, the band guidance is so setup, that in the transport direction (arrow of TR) of the fiber band FB, a band guide element FE2 is placed after the band monitor BW2. The guide element FE2 is vertical to the plane of the base of the feed apparatus Z. The function of the guide element FE2 is not diminished if it is turned out of the vertical position, although it possesses a tendency toward the vertical position. An advantage is that the guide element FE2 is designed as a rod. However, other configurations are conceivable, which make possible a contact surface with the fiber band. The rod is affixed to a supporting element of the feed apparatus Z.
The rod can be placed in a horizontal position (arrow w) at right angles to the transport direction of the fiber band FB. In this way, a change of direction of the fiber band FB in relation to the original transport path can be carried out. A common adjustment for band monitor BW2 and guide element FE2 can be achieved through the adjustment of the support element in the direction v.
By means of this band guidance, the fiber band has not only a contact surface on the band guide BF but also attains a contact surface with light pressure on the guide element FE2. Between the band guide BF and the guide element FE2, the fiber band runs in an advantageous manner without marked vibration. The achieved damping of the originally strongly vibrating fiber band makes possible a supervision of the fiber band without a false signal emanating from the band monitor BW2.
Another embodiment is shown in FIG. 6. In this case the band monitor BW3 is placed in the area of the band guide BF. Relative to the transport direction of the fiber band FB, the band monitor BW3 is disposed in front of the band guide BF. The other guide element FE3 is in the area of band monitor BW3 and again relative to the direction of transport of the fiber band FB said guide element FE3 is before the band monitor BW3. The guide element FE3 is constructed as a ring. Band monitor BW3 and/or another guide element FE3 are adjustable as to position relative to the transport direction arrow of the fiber band FB. This design brings about the effect, that the fiber band is substantially damped in its vibration, so that faulty signals from the band monitor BW3 are avoided. A false signal arises, if, by means of excessive vibration, the fiber band is moved out of the range of the sensor surface SF. In this case, the band monitor can identify no fibers.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention. It is intended that the present invention include such modifications and variations as come within the scope of the appended claims and their equivalents.
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The invention concerns a textile machine operating on fiber band with a feeding device for the fiber band and a guide element for the fiber band and further provided with a band monitor for the discovery of band breakage. The band monitor (BW, BW1, BW2, BW3) is placed always in the area of the guide element, in particular one band guide (BF) and another band guide element (FE, FE1, FE2, FE3) in the area of the band monitor (BW, BW1, BW2, BW3). The running time behavior of the fiber band (FB) is directly improved by the guide element (FE, FE1, FE2, FE3), that is, the vibrations of the fiber band (FB) are damped. This will avoid a situation wherein false alarm signals are given because of an originally vibrating fiber band at the band monitor.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to floorcare appliances, and more particularly, relates to a full bag indicator to be used with such an appliance.
2. Description of the Prior Art
Full bag indicators have been long known in the floor care appliance art, such indicators taking a variety of configurations. A problem exists, however, relative to the calibration of these full bag indicators. This has been solved by the use of, for example, a threaded valve member which moves into and out of an aperture leading to the indicator so that the atmospheric pressure flow to which the full indicator is subjected may be varied to obtain an operative, relatively accurate structure mounted with floorcare appliance.
Although the use of such a means as known provides a satisfactory operation for the full bag indicator, a differing kind of calibration adjustment which more easily leads to an inexpensively manufactured full bag indicator would be advantageous.
Accordingly, an object to this invention to provide a calibration arrangement for a full bag indicator which is inexpensive.
It is a further object of this invention to provide calibration of a full bag indicator configuration which may be easily had on the manufacturing floor.
It is a still further object to provide a full bag indicator which may be mounted so as to slide along a floor care appliance as it is mounted to an aperture providing air flow to the full bag indicator to thereby permit calibration for accurate readout.
BRIEF SUMMARY OF THE INVENTION
A full bag indicator is preferably mounted in the lid of a cleaner on the underside thereof in a well which borders the rim of the full bag indicator both longitudinally and laterally. A clamp configuration attaches the full bag indicator in the well and is situated to permit longitudinal sliding of the full bag indicator as the same as calibrated.
The full bag indicator has a configuration of an open box having a top, sides and ends which are integral. A bottom is included which closes off the open side of the box like configuration to provide a closed compartment for the full bag indicator for a piston mounted within the compartment of the full bag indicator. The piston includes a spring attached to it which tends to urge the piston against the flow surge of atmospheric air which is imposed on it. The spring is attached to one end of the full bag indicator case for this purpose so as to be tensioned by the flow of atmospheric air. An integral pin forms the attachment of the spring to the box like configuration. At the spring end of the box like configuration is an aperture extending into and communicating with the confines of the full bag indicator box like configuration or case and imposing a pressure on the head of the piston. This aperture communicates with an aperture extending through the lid of the cleaner or the like, with an upstanding portion of the full bag indicator case extending through this aperture. The aperture is larger than the upstanding portion of the full bag indicator case so that movement of the full bag indicator case along the aperture relative to the clamp opens and closes the case aperture. Thus, calibration of the full bag indicator is had by varying atmospheric pressure flow to the full bag indicator by moving its case longitudinally along the aperture extending through the bag lid.
The opposite end of the full bag indicator case includes an aperture which communicates with the vacuum system of the floor care appliance so that the combination of this negative pressure and adjustment of the aperture leading to the indicator for the passage of atmospheric pressure flow past the piston gives a reading of full bag condition when the full bag indicator is properly calibrated relative to the aperture extending through the bag lid.
A gasket is disposed around a peripheral portion of the full bag indicator case to seal the full bag indicator case from leaks and additional atmospheric pressure flow to it other than afforded by the aperture provided.
The bottom piece of the full bag indicator case may be of green material while the piston may be red. At the same time, the indicator case, itself, can be transparent. Movement of the piston of the full bag indicator to indicate a full bag condition covers the green of the bottom piece as it moves below the viewing portion of the full bag indicator. This gives a visual readout of full bag conditions and alerts the user of the cleaner that it is time for changing the bag.
BRIEF DESCRIPTION OF THE DRAWINGS
Reference may now be had to the accompanying drawings illustrative of the invention, both as to its organization and function, with the illustration being of the preferred embodiment but being only exemplary:
FIG. 1 is a perspective view of a cleaner including the full bag indicator of the instant invention;
FIG. 2 is a central cross sectional view of the full bag indicator and bag lid;
FIG. 3 is a cross sectional view of the invention taken along line 3--3 of FIG. 2;
FIG. 4 is a perspective view of the full bag indicator in a demounted condition;
FIG. 5 is a partial perspective view of the underside of the bag lid showing the clamp which holds the full bag indicator in position;
FIG. 6 is a cross sectional view of the full bag indicator taken on line 6--6 of FIG. 2;
FIG. 7 is a view similar to FIG. 2 but showing the full bag indicator in another adjusted position.
DETAILED DESCRIPTION OF THE INVENTION
Turning now to FIGS. 1 and 5, it can be seen that a cleaner 10 having a bag lid 12 which may be hinged (not shown) to the remainder of the cleaner 10 so as to be movable to an upward position to permit ingress to a bag cavity (not shown). The cleaner 10 includes an on and off switch 14 and wheels 15,15 (only one shown) which rollingly mount the cleaner 10 during the cleaner operation. A full bag indicator 16 mounted on the lid 12 with the cleaner 10 extends through the lid 12 of cleaner 10 so as to provide a readable means for indication of bag condition. The full bag indicator 16 is mounted in a depression or well 18 on the underside of bag lid 12 and is clamped in this position by a clamp 20 which extends around the bottom and sides of the full bag indicator 16 to engage against a bottom 22 of the full bag indicator 16 to hold the bag indicator 16 against the bag lid 12. The clamp 20 is held against the bottom 22 of the full bag indicator 16 by means of a screw 24 which mounts in a boss 26, integral with the bag lid 12.
Turning now to the remaining figures in the Drawing, it can be seen that the well 18 extends completely around the full bag indicator 16 providing a flat face 28 bordered by short vertical end walls 30,32 and side walls 34,36. It should be clear that, in view of the spacing of end walls 30 and 32, that the full bag indicator 16 has a certain amount of play therebetween and may be capable of being moved between the stops formed by these two end walls. A gasket 38 extends around the depression or well 18 by being captured within an integral rim 40 which extends around upper portion of the full bag indicator 16. The rim 40 is comprised generally of end walls 42 and 44 and side walls 46 and 48. The gasket 38 is trapped within this rim against the flat face 28 of depression or well 18 when the full bag indicators 16 is mounted by means of the clamp 20 to the bottom side of the full bag lid 12.
As set out previously, the full bag indicator is comprised of an open boxed configuration 50 and the bottom 22. The box like configuration 50 includes end walls 54 and 56 and side walls 58 and 60. A top 62 is also provided for this box like configuration 50, including an upwardly disposed portion 64 which serves as the viewing window for the full bag indicator 16, with this step portion 64 extending through an aperture 66 formed in the bag lid 12 of the cleaner 10. This step portion 64 is that portion of the full bag indicator 16 seen in FIG. 1.
The aperture 66 is somewhat larger than the upstanding step portion of 64 so as to provide an entrance port 68 for the entrance of a flow of atmospheric air to the internal portions of the full bag indicator 16. This entrance port 68 extends essentially across the width of the step portion, with the gasket 38 abutting the sides of the step portion 64 terminating the entrance port 68 and sealing off atmospheric air entrance to the internal portion of the full bag indicator 16 by any other means than the entrance port 68. It is noted that the gasket 38 seals generally the sides and terminating ends of the full bag indicator 16 away from the entrance port 68.
The end walls 42, 44 and side walls 46 and 48 of the rim 40 of the full bag indicator 16 essentially space the same from the bag lid 12 on its underside to provide a flow passageway from the entrance port 68 to the end of the full bag indicator 16 provided with another port 70. It permits entrance of atmospheric air flow through a chamber 72 of full bag indicator 16 causing an expansion or extension spring 74 to expand. This tends to move a piston 76 of the full bag indicator 16 against the imposition of spring force from spring 74.
The coil spring 74 is mounted within the piston 76 by means of a pair of integral clevis like or yoke pieces 80 and 82 which are mounted on the opposite sides of a spring end 78 of spring 74 and being spaced sufficiently apart as to permit the spring end to extend therebetween. Thus, tending to align the spring end and at the same time permitting attachment of it to them by means of a pin 84 which extends through bores 81 and 83 in yoke pieces 80 and 82, respectively.
The opposite end of the spring 74 is mounted with the box like configuration 50 by means of an integral pin 86 which extends downwardly medially of the width of the box like configuration 50 with a loop spring end 88 of a spring 74 permitting insertion of the spring over the pin 86 so as to provide its opposite tension point. It will be noted that the spring end 78 and 88 are mounted 90° relative to one another. This also tends to align and maintain the spring in proper operationing position.
At the opposite end of the full bag indicator 16 at end wall 54 a rectangular hole 90 is provided adjacent its bottom and medially of the width of the box like configuration 50. This opens to the pressure in the bag cavity so that operation of the cleaner 10 tends to provide a force against the piston 76 to move it against the tension in the spring 74 to move the piston 76 towards the end wall 54. Such movement is shown in dashed lines in FIG. 2.
The bottom 22 of the full bag indicator 16 closes off the box like configuration 50 to seal the same and provide the afore mentioned chamber 72. It has a step configuration 92 so as to provide an easily assemblable connection with the box like configuration 50. The bottom 22 also includes upstanding pin 94,96 that extend upwardly in assembled condition on opposite sides of the pin 86 and abut the bottom side of spring end 78 to maintain the spring 74 in its assembled relationship with the open box like configuration 50. The bottom 22 is sonic welded to the open box like configuration 50 to provide an airtight condition between the two.
It should now be apparent how the full bag indicator 16 may be calibrated with maximum efficiency and without great difficulty. Entrance of atmospheric air through the port 68 works with the vacuum pressure provided through the port 90 tending to move the piston 76 under the step portion 64 of the top 62. In order to calibrate the full bag indicator 16 for a given vacuum indicating pressure, variances of atmospheric air flow through the port 68 is obtained by moving the full bag indicator leftwardly or rightwardly along the bag lid well, the clamp 20 only maintaining the full bag indicator in its fixed position during use of the cleaner and not preventing movement of the full bag indicator 16 when the same is urged by hand or by the use of a forcing tool in a linear direction against the full bag indicator along the bag lid 12. Such movement varies the dimensions of the port 68 relative to its width moving the top 64 closer to or further away from the abutting edge of the lid 12. this, then limits the amount of flow of atmospheric air to the chamber 72, reducing or increasing the atmospheric air pressure or the pressure differential on the piston 76, based on the flow past the piston 76 to vacuum pressure of the cleaner 10 versus the flow of atmospheric air from the port 68. Calibration of the full bag indicator 16 may thus be had easily and conveniently without the resort to things such as screw valves or the like.
Ideally the open box like configuration 50 may be made of transparent material to provide a viewing window through the step portion 64. At the same time the piston may be red to give an indication when the same is under the window of a full bag condition in the vacuum cleaner 10. During the period while the piston 76 is not beneath the window formed by the upstanding portion 64 a green bottom 22 provides a safe operating indication.
From the foregoing description it should appear clear that a full bag indicator arrangement has been provided which it easily calibrated by merely adjusting its mounting relative to the structure with which it is associated. It should also be clear that many modification would occur to one skilled in the art which would fall within the scope and purview of the description offered.
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There is provided a full bag indicator which is calibrated by movement of it along the structure it is mounted to, to thereby vary an aperture leading into the full bag indicator.
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BACKGROUND OF THE INVENTION
The present invention relates to a method and associated apparatus for encoding an analog signal into a digital form and for decoding the digital signal back into an analog form, wherein the encoding and decoding are performed in such a way as to maximize the useful dynamic range of the signal when used for encoding and decoding an audio signal.
Digital encoding of analog signals is usually accomplished by what is called a "linear" conversion, in which a simple direct binary value equal to the analog value to be encoded is generated. For example, an 8 bit digital system would encode all input analog signal values into one of 256 values linearly related to the input analog value. The conversion of the input analog signal into its binary representations takes place at a rate equal to at least twice the rate of the highest frequency component to be encoded within the analog signal. Because of the finite and limited number of representations possible using a binary number, the input signal is "quantized" and the representation at each sample may not accurately correspond to the associated analog value. For instance, if the encoding system is an 8 bit system, there are only 256 values possible, i.e. 0 through 255; or, more specifically in binary representation, 00000000 through 11111111. If the input analog value sampled were 128.438, for example, it would be represented by the nearest binary value, e.g. 1000000 or 128. The difference of 0.438 is an error often referred to as the "quantization error" or "quantization noise". When the analog signal being converted is an audio signal, this error is heard as noise when the signal is decoded back into its analog form. When the analog signal is large, the error represents only a small fraction of the overall signal value. When the signal is small, however, the error becomes much more significant. In fact, signals smaller than the quantization size are lost entirely.
One solution to this problem has been the use of non-linear digital encoders/decoders such as those commercially sold by Precision Monolithics, Inc. under the trademark COMDAC. The principle of operation of the COMDAC encoders/decoders is to make the step size dependent on the signal amplitude. As a result, for small signals the quantization noise is smaller and, therefore, less objectionable. At the same time, the quantization noise for large signals is correspondingly larger, and is adequately "masked" in the case of audio signals by the large signal itself. While the performance of the COMDAC device is acceptable for some uses, the general approach is inadequate for high fidelity audio use.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a method and associated apparatus for digital/analog encoding and decoding which exceeds the dynamic range of COMDAC devices while, at the same time, minimizes the effects of quantization noise.
It is another object of the present invention to provide a method and apparatus for digital/analog encoding and decoding which, while providing improved performance, does so in an efficient and economic manner.
It is yet a further object of the present invention to provide a method and apparatus for digital/analog encoding and decoding which is particularly adapted to audio signal encoding and decoding and will reduce noise to a level acceptable to persons having stringent requirements.
The foregoing objects have been realized by encoding/decoding apparatus performing the method of the present invention which comprises the steps of pre-emphasizing the analog signal to accentuate its high frequency components; successively sampling the pre-emphasized signal; encoding the samples non-linearly to create a series of digital representations of the samples having a lower order resolution than the sample resolution; obtaining the differences between the samples and their corresponding lower resolution digital representations; and combining each sample prior to encoding with the difference measurement for the previous sample. The encoded signal is then decoded in a non-linear complementary manner and converted to analog format to create an approximate analog output signal. This is followed by a deemphasis step which is complementary to the pre-emphasis to produce an analog output signal closely approximating the original analog input signal.
Both fully digital and hybrid analog/digital implementations of the present invention are possible and are disclosed with possible variations. In the fully digital embodiment the samples are converted to a digital format having a higher resolution than the series of digital representations. The digital representations are obtained from the digitally formatted samples, and the difference measurements are combined with the samples in their digital format. In the hybrid embodiment the difference measurement is combined with the pre-emphasized analog signal prior to sampling, and the samples are obtained from the combined analog signal and difference measurements.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block-diagram of a hybrid encoder according to the present invention.
FIG. 2 is a block diagram of a hybrid decoder according to the present invention.
FIG. 3 is a block diagram of a full digital non-linear encoder according to the present invention.
FIG. 4 is a block diagram of a full digital non-linear decoder according to the present invention.
FIG. 5 is a graph showing the characteristics of a preemphasis filter as incorporated into the present invention.
FIG. 6 is a circuit diagram of an analog non-linear decoder circuit as incorporated into the present invention.
FIG. 7 is a circuit diagram of an analog non-linear encoder circuit as incorporated into the present invention.
FIG. 8 is a block diagram of a hybrid encoder according to the present invention incorporating a predictor therein.
FIG. 9 is a block diagram of a hybrid decoder according to the present invention incorporating a predictor therein.
FIG. 10 is a block diagram of a digital implementation of a predictor hybrid decoder according to the present invention.
FIG. 11 is a block diagram of a digital implementation of a predictor hybrid according to the present invention.
FIG. 12 is a more detailed block diagram of a digital encoder/decoder system according to the present invention.
FIG. 13 is a graph illustrating the transfer functions of various elements in the system of FIG. 12.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention accomplishes its objectives by using a non-linear encoding method with an error carryback technique and high frequency pre-emphasis of the analog signal before encoding. The analog signal to be encoded digitally is first pre-emphasized; that is, the high frequencies are selectively accentuated. The signal is then encoded into digital form in a non-linear analog to digital (A-D) encoder. The non-linearity may be provided by either analog or digital means. The difference between the analog equivalent of the resultant non-linear digital representation and the input analog signal is measured and added to the next sampled analog value to be encoded. For decoding, the digital representation is applied to a non-linear decoder which is complementary to the non-linear encoder used in the encoding processes. Again, this non-linear characteristic may be accomplished either digitally or by analog means. Finally, the signal is passed through a de-emphasis circuit which is complementary to the pre-emphasis circuit used in the encoding process.
Two functionally equivalent forms of the present invention are described hereinafter. They differ only in the method whereby the non-linear digital encoding is achieved. One is fully digital and one is a hybrid digital/analog method.
The hybrid encoder is shown in FIG. 1. The input analog signal is applied to the pre-emphasis circuit 11 which emphasizes the high frequencies in the signal. The pre-emphasized signal is passed to the analog adder circuit 12, where the residual quantization error from the previous encoded sample is added to it. Sample and hold circuit 20 samples and holds the result and passes it on the sample and hold circuit 13. Two sample and hold circuits are necessary to prevent the resultant sum from adder 12 from immediately effecting itself instead of the subsequent sample. The sampled and held signal is applied to the input of the standard linear analog to digital converter 15 through the non-linear circuit 14. The output of A-D converter 15 is the digitally encoded output of the system. This digital signal also is passed to the linear digital to analog circuit 18 whose output passes to the non-linear circuit 17. The functions of non-linear circuit 17 are selected to be exactly complementary to the functions of the non-linear circuit 14. The result is that the output of non-linear circuit 17 is the quantized analog representation of the input analog signal. This signal is subtracted from the input signal by the difference circuit 16 and the resultant signal added to the next analog signal value to be sampled by the adder circuit 12. Note that D-A circuit 18 may be the D-A circuit within the A-D circuit 15.
The anti-aliasing filter 19 limits the upper frequency limit of the input analog signal to one-half the sample rate of the digital encoder as is standard in digital encoding systems.
The hybrid decoder is shown in FIG. 2. The digital signal from the encoder is converted to an analog signal by the linear digital to analog converter 21 and passed through the non-linear circuit 24 which is identical to the non-linear circuit 17 of FIG. 1. It is complementary in functions to non-linear circuit 14 in FIG. 1. The output on the non-linear circuit is passed to post filter circuit 23 and then to de-emphasis circuit 22. De-emphasis circuit 22 de-emphasizes high frequency in a fashion complementary to the pre-emphasis of pre-emphasis circuit 11 in the encoder of FIG. 1. Post filter 23 is similar to antialiasing filter 19 of the encoder. It removes all frequencies beyond the upper frequency of the original analog signal passed by anti-aliasing filter 19 of FIG. 1. For best performance of the overall system, the A-D and D-A converters used in the encoder and decoder must be matched and, have high accuracy.
Implementation of the encoder of the present invention in a full digital manner is shown in FIG. 3. The input analog signal is frequency limited by anti-aliasing filter 31. As usual, this filter restricts the upper frequency limit of the input analog signal to less than one half the sample frequency of the A-D conversion part of the system. Pre-emphasis filter 32 selectively amplifies high frequencies as was the case in the hybrid encoder of FIG. 1. For critical applications the preemphasis filters should be adaptive. That is, it should adjust the amount of pre-emphasis of high frequencies in response to the amount of high frequency signal present. The greater the amplitude of the high frequency components, the more the high frequency boost is reduced. Such adaptive pre-emphasis filters are well known in the art; the "Dolby" noise reduction type B is a typical example. If such an adaptive pre-emphasis filter is used, a complimentary filter must be used in the decoder. For less stringent applications, pre-emphasis filter 32 may be a single pole, i.e. 6 db/octave, filter designed with the slope up beginning between 200 and 1 KHz and leveling off in a shelf between 4 KHz and 10 KHz as shown in FIG. 5. A fuller explanation of the reason for this filter will follow later herein.
The output of the pre-emphasis filter passes on to the sample and hold circuit 33. Circuit 33 holds the sampled analog value while the A-D converter circuit 34 converts it to a linear digital representation. In the present invention, the A-D converter 34 is a high resolution converter. For example, converter 34 may be a 16 bit converter even though the final output digital signal of the system is 8 bits. Circuit 35 is a digital adder where the high resolution digital representation of the analog signal is added to the residue or difference between the 8 bit non-linear representation sent out as the output digital signal and the exact value of the previous sample. Circuit 36, which is designated as the non-linear encoder difference generator is, in the preferred embodiment, implemented as a dual look up table or memory. The high resolution (i.e. in the example, 16 bit) digital sum of the current sample plus the residue from the previous sample act as the address of the memory. At that "address" are two digital words. One is the closest non-linear digital representation of the sum. The other is the linear representation of the difference between that non-linear representation value and the input sum or address. The output digital signal is the non-linear digital representation and the difference is the digital signal carried back to the adder 35.
The function of circuit 36 can best be described and under stood with reference to the 8 to 4 bit encoder example shown in Table 1
TABLE 1______________________________________8 BIT DIGITAL SIGNAL ENCODED INTO A 4 BITREPRESENTATION USING THE PRESENT INVENTION______________________________________128 864 732 616 58 44 32 21 1-1 -1-2 -2-4 -3-8 -4-16 -5-32 -6-64 -7-128 -8______________________________________
Table 1 shows in column 1 some sign-magnified decimal values of an 8 bit linear representation of an analog signal ranging from +128 to -128. The next column gives the 4 bit non-linear decimal representation of these values. The encoding is simple for the values +/-1 and +/-2. They are encoded to their same value, i.e. +/-1 and +/-2. 8 bit values greater than or equal to 2 and less than 4 are also encoded to the 4 bit non-linear representation 2. The linear value 3 would be represented by the non-linear value 2 with a residue of 1. As another example, the linear 8 bit value of 23 would be represented by the nearest 4 bit non-linear representation 5, which equals 16 with a residue of 7. This encoding is a quasi-logarithmic encoding and is useful for encoding audio signals using this method because it takes advantage of the psychoacoustic phenomenon known as masking. Louder signals can mask or conceal larger errors or noise. Note that with this encoding method the encoding errors or residues tend to be proportional to the signal value.
The full digital decoder for the full digital encoder shown in FIG. 3 is shown in FIG. 4. The low resolution, non-linear digital signal is applied to a memory 41 as the address in a manner similar to that used in the encoder circuit 36. The output of the memory is a high resolution digital representation applied to the high resolution decoder 42. For instance, the encoded signal may be an 8 bit non-linear representation. The memory 41 would have 256 locations, each with a 16 bit word stored therein. That 16 bit would be the linear 16 bit representation of the 8 bit non-linear value used as its address. This 16 bit linear digital value is then converted into the analog signal by the 16 bit linear D-A converter 42. Post filter 43 then removes all signal components outside the desired signal spectrum. De-emphasis circuit 44 is complementary to the preemphasis circuit 32 in the encoder shown in FIG. 3.
The general example discussed above involved using the present invention to encode a 16 bit linear digital representation into an 8 bit form and subsequently decode it back into a 16 bit digital form and then to an analog form. The specific example of Table 1 was for an 8 bit linear representation encoded into a 4 bit form. The method of the present invention can generally be applied to encoding any higher resolution digital representation of an analog signal into a low resolution nonlinear form and recovering it. It is particularly applicable to audio signals where noise and errors proportional to signal size are more tolerable.
Table 2 illustrates the fully digital encoding and decoding implementation of the present invention as employed with the 8 bit to 4 bit example previously discussed with relation to Table 1.
TABLE 2__________________________________________________________________________ILLUSTRATION OF FULL DIGITAL8-4-8 BIT DECODERRow__________________________________________________________________________ ##STR1##__________________________________________________________________________
Row 1 of Table 2 gives a series of 8 bit linear values to be encoded using the present invention. Row 2 is the sum of that value plus the residue left from the previous encoding quantization. Row 3 is the 4 bit non-linear representation of the sum. Row 4 is the residue or difference between the linear value associated with the 4 bit representation and the actual sum it is representing. Row 5 is the decoded, linear representation of the 4 bit non-linear representation. Finally, Row 6 is the resultant error. The content of the encoding and decoding memories 36 and 41 should be evident from this illustration. Various forms of non-linear encoding may be used in particular situations; but, in all instances, the digital output of 36 will be a reduced number of bits compared to its input and each of those non-linear representations will map back into specific higher resolution input values. The linear residue output 37 of the difference generator 36 is equal to the digital difference between that linear input value and the non-linear representation value decoded back to linear form.
Using this method of error or noise carry back with non-linear encoding causes highly accurate cancellation of accumulated errors at zero crossings, which results in a strong suppression of noise components at and below the principal frequency components of the encoded signal. This occurs because the quantization step size is small near zero because of the non-linear encoding. This is a very important benefit of the present invention. Because of this, it is appropriate to pre-emphasize the higher frequencies in the original analog signal to take advantage of this suppression of lower frequency noise. For best results the pre-emphasis should be adaptive as disclosed earlier. This explains the need and form of the pre-emphasis circuits 22 of FIG. 2 and 32 of FIG. 3.
The hybrid and fully digital forms of the present invention can be used together--often to good advantage. For instance, a fully digital implementation of the encoder may be used with a hybrid implementation of the decoder. To accomplish this, the non-linear function 24 shown in the hybrid decoder of FIG. 2 would be mapped into the digital memory 36 used in the fully digital encoder of FIG. 3. A hybrid non-linear circuit is often desirable because of its simplicity and reduced cost in the decoder. An example of a non-linear circuit usable in a decoder is shown in FIG. 6. Diodes 62 and 63 are the non-linear elements. With resistor 61 small and resistors 64 and 67 large, the system becomes essentially an exponential decoder. Note that diodes 62 and 63 are conventional semi-conductor diodes with an exponential current to voltage relationship. Resistor 61 sets the maximum slope or gain of the encoder while resistor 64 sets the minimum slope or gain. Resistor 65 sets the overall gain of the decoder circuit while 66 indicates a conventional operational amplifier. Resistor 67 acts with resistor 61 to form a voltage divider to reduce the input signal levels and impedances to the 1/2 volt range usable with typical diode non-linear elements.
The non-linear decoder circuit shown in FIG. 7 is complementary to the circuit of FIG. 6. Resistor 72 should equal 64, 73 should equal 61, 71 should equal 65 and 67 should equal 72. The remaining components 74-77 are also of similar designation. It should be noted that the circuit shown in FIG. 6 could be used as circuit 17 of FIG. 1.
A special case of the present invention is one in which the error residue carried back is set at zero. The benefit of reduced low frequency noise reduction is lost in this case but one gains the benefit of simplicity in the encoder. Whether or not error carryback is used in the encoder, the same decoder is usable. Thus, for those applications demanding highest performance and capable of justifying the added cost, the carryback technique may be used; but, it may be dispensed with in less critical applications and yet remain compatible with the same playback decoder.
While the pre-emphasis and de-emphasis circuits 11 and 22 of FIGS. 1 and 2 were discussed in some detail previously, they warrant further consideration. Because of the error carryback technique and non-linear encoding of the present invention, low frequency noise is substantially suppressed and shifted to higher frequencies. Therefore, the pre-emphasis of high frequencies before encoding and de-emphasis after decoding makes best use of this benefit. There is another important benefit of the present invention when considered more generally. Note that when the encoded signal is small, the accuracy of the encoded representation is higher than it is when the signal is large. If a precircuit is used which minimizes the input signal in general, the encoding will be more accurate. A simple approach to this problem is to have a pre-circuit which passes only the difference between the current sample and the previous sample. This is a differentiating or differentiator circuit. The pre-emphasis circuit described previously herein is a form of differentiator. It is modified at very high and very low frequencies to make its effect less radical.
More elaborate "predictor" circuits as known in the art can be used to great advantage as part of the present invention. A generally useful class of such predictors is one based on the derivatives of the input signal. In a simplified system, the predictor predicts what the next sample is by forming a linear combination of the derivatives of the samples up to that time. If the sample to be predicted is T -0 and the previous sample is T -1 , and the one before that T -2 , etc., a 0th order predictor-would predict that:
T.sub.0 =T.sub.-1
while a 1st order predictor would predict that:
T.sub.0 =T.sub.-1 +T.sub.-1 -T.sub.-2 =2T.sub.-1 -T.sub.-2
thus, taking into account the rate of change of the first derivative of the signal.
A second order predictor might predict that:
T.sub.0 =3T.sub.-1 -3T.sub.-2 =T.sub.-3
thus, taking into account both the first and second derivatives of the signal.
The use of a general predictor with the present invention's hybrid encoder is shown in FIG. 8. The input analog signal is added to the residue error carryback in adder circuit 81. Sample and hold circuit 82 samples and hold the current value of the analog signal. Predictor 83 outputs its prediction of the current value based on the previous sampled values as described above. Difference circuit 84 outputs the difference between the actual current value and the predictor's prediction to the nonlinear circuit 85. 86 is a linear A-D converter whose output is the non-linear encoded predictor differenced digital signal. This signal is converted back into the quantized linear for of the difference signal by; D-A converter 87 and non-linear circuit 88. This difference is added to the predictor signal from predictor 810 by adder circuit 89 to output a replica of the original signal to difference circuit 811. The output of circuit 811 is the difference between this reconstructed quantized signal and the correct original signal which is carried back and added to the next sample by adder 81.
A hybrid decoder according to the present invention and employing a predictor is shown in FIG. 9. The input digital signal from the encoder is converted to analog form by linear D-A converter 91. This signal is passed through the non-linear circuit 92 to adder circuit 93 where it is added to the predictor 94 output resulting in the output analog signal. Note that predictors 83, 810 and 94 are identical in operation. These predictors must be stable; that is, not susceptible to oscillation or lockup and must converge. These requirements and how to attain them are well known to those skilled in the art and, therefore, in the interest of simplicity, will not be addressed further herein. Note that in the encoder, the function of elements 81, 83, 84, 85, 86, 87, 88, 89, 810 and 811 can all be achieved in a relatively simple fully digital processor, making the digital implementation of the present invention using a predictor much simpler than the hybrid example shown.
In the case of the fully digital encoder as shown in FIG. 10, the input analog signal is converted to a high resolution linear digital form by A-D converter 101 (which can be the A-D converter 21 of FIG. 2). The exact functions defined in Figure 8 are then all performed digitally by the digital processor 102. A standard microprocessor can be used for this function.
Similarly, in the digital implementation of the predictor decoder of FIG. 11, a digital processor 111 performs the predictor functions, summing functions, and table lookups described previously for the digital implementation of the decoder and passes on the high resolution digital representations to the linear D-A converter 112 for conversion to the sampled output analog signal.
FIG. 12 is a more detailed block diagram of the digital encoder/decoder system. Elements which are the same as in previous drawings are identified by the same reference numerals. Analog-digital encoder 34 converts the input analog samples into 16 bit digital representations. Adder 35 is a 16×16 device adapted to produce a 16 bit sum output from two 16 bit inputs. The output of adder 35 is delivered to an address register 39, which loads the word and provides a one-word delay for the signal subsequently fed back to adder 35. The address register 39 outputs a 16 bit address signal to a lookup table 37, which stores 8 bit words corresponding to each of the 65,536 possible 16 bit inputs. Lookup table 37, which may be implemented as a ROM, provides an 8 bit output which most closely approximates the 16 bit input. Since the resolution of the 16 bit words is 256 times that of the 8 bit output words, lookup table 37 provides the same 8 bit word for each set of 256 successive 16 bit input words (except for the first and last 8 bit words, which each have 128 corresponding 16 bit inputs).
The 8 bit output digital signal from lookup table 37 is transmitted to the receiver, where it is delivered as an address to the non-linear memory 41 in the form of a decoder lookup table. This lookup table stores 256 16 bit words, and converts the 8 bit input signals to 16 bit output signals for application to digital-to-analog converter 42. Decoder lookup table 41 is generally complementary to encoder lookup table 37. However, the 16 bit output from decoder lookup table 41 will generally not be exactly the same as the 16 bit input to encoder lookup table 37 because the decoder lookup table only receives 8 bit input information, and therefore has no way of knowing the precise 16 bit signal at the input to encoder lookup table 37. For each 8 bit input signal to the decoder lookup table there are 256 possible 16 bit outputs, and the memory cannot determine which one of these possible outputs corresponds to the actual 16 bit input to the encoder lookup table 37. Accordingly, the 1-6 bit output from decoder lookup table 41 is arbitrarily selected from one of the 256 possible outputs corresponding to each 8 bit input; in the preferred embodiment the 16 bit words placed in the lookup table 41 are selected to be the midpoints of each successive set of 256 16 bit words. Thus, lookup table 41 skips 255 possible words between each 16 bit word that is actually stored. In this way only one 16 bit word in the table will correspond to each of the possible 8 bit input signals.
In the process of reducing the 16 bit input to encoder lookup table 37 down to 8 bits and then expanding it back to 16 bits in decoder lookup table 41, there will thus be a difference or error between the inputs to table 37 and the outputs from table 41 (except for one in each 256 inputs). However, since for each input the outputs from the encoder and decoder lookup tables are known, the error produced for each 16 bit input to encoder lookup table 37 will also be known in advance. These error amounts are stored in an error lookup table 38 which is also addressed by the same signal that addresses encoder lookup table 37. Thus, for each 16 bit input sample, an 8 bit output signal will be produced by encoder lookup table 37, while the predicted error between the 16 bit input and the corresponding 16 bit output from decoder lookup table 41 is produced by error lookup table 38. This predicted error, the production of which is delayed by a one word interval by address register 39, is fed back to adder 35, where it is added to the next 16 bit input sample.
This arrangement is illustrated graphically in FIG. 13. The 16 bit outputs of adder 35 and decoder lookup table 41 are plotted along the horizontal axis, while the 8 bit output from encoder lookup table 37 is plotted along the vertical axis. The described system encompasses a total of 65,536 different 16 bit words, and 256 different 8 bit words. Each 8 bit word corresponds to 256 successive 16 bit words, as illustrated by the exaggerated step function 120. The encoding and decoding transformations are non-linear but symmetric about the origin.
Assume first that a 16 bit input 121 addresses lookup table 37. The lookup table will produce a corresponding 8 bit encoded output signal 122. It should be noted that there are 256 different 16 bit inputs which would have produced the same 8 bit output; these 16 bit inputs are all included within the dashed lines on each side of 8 bit step 122. Since decoder lookup table 41 does not know which of the 256 different possible 16 bit inputs produced the particular 8 bit output, it arbitrarily selects the median 16 bit word 123 within this range as its output. The difference (error) between this midpoint 123 and the actual 16 bit input 121 is indicated in FIG. 13 and is delivered from error lookup table 38 to modify the next 16 bit input to adder 35.
In the preferred embodiment EPROMs are used as the memory elements. These devices are quite expensive, and collectively can represent the major cost of the system. The described transformation from 16 bits down to 8 bits, and then back again to 16 bits, halves the number of EPROMs required as compared with a full 16 bit system, and also allows the capacity of the transmission system to be halved.
While specific embodiments of the invention have been shown and described, numerous variations and alternate embodiments will occur to those skilled in the art. Accordingly, it is intended that the invention be limited only in terms of the appended claims.
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Apparatus and an associated method are described for encoding an analog signal to a digital representation thereof and then decoding the same to reconstruct the original analog signal with reduced quantization noise and error. The analog signal is first adaptively pre-emphasized. A series of samples of the pre-emphasized signal are then obtained and encoded to create a series of digital representations which have a lower order resolution than the samples. The difference between each sample and its corresponding lower resolution digital representation is obtained and combined with the next sample. Decoding of the combined signals takes place in a complementary manner to create an approximate analog output signal, which is then de-emphasized in a manner complementary to the pre-emphasis to produce an analog output signal closely approximating the original analog signal. In a fully digital implementation the samples are converted to a digital format with a higher order resolution; the digital representations are obtained from the digitized samples, and the difference measurements are combined with the samples in their digital format. In a hybrid digital/analog implementation the difference is combined with the analog signal prior to sampling.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed to a medical imaging system of the type operable in a modality for acquiring images, and having means for processing the images, means for the transmission of the images and means for storing the images including a number of separate memories.
2. Description of the Prior Art
The book “Bildgebende Systeme für die medizinische Diagnostik”, edited by H. Momeburg, 3 rd Edition, 1995, pages 689 ff. discloses that image and data sequences associated with one another be respectively stored in a specific memory system in medical image systems. A problem with this generalized approach is that spontaneously occurring load peaks, that negatively influence the entire system arise within a networked system. It is also disadvantageous that all data of a given procedure are lost given outage of a memory.
Previous memory cluster solutions together with RAID technology already offer very high technical dependability and high performance, however, there are dependability gaps and performance bottlenecks at the application level in a networked environment. Imaging systems will be increasingly employed for small and mid-sized applications. Economical systems that enable system dependability, failsafe operation and high system performance with standard components are required therefor.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a medical imaging system of the type initially described, which enables a good load distribution and dependable storage over the-entire imaging system.
This object is inventively achieved in an imaging system having a number of memory systems and a control system, which controls storage of the image data in the memory systems that is fashioned such that successive image datasets are stored in separate memory systems. A medical image system having self-controlled, distributed storing is thereby obtained. The distribution of the loads onto different memory systems results in peak loads being avoided. Moreover, in the case of brief-duration or longer-lasting outage of a memory system, the data can be rerouted automatically to other memory systems, so that no data jam (backlog) arises.
In an imaging system, the memory systems are-classified in memory hierarchies. On-line memories with disk storage units in RAID technology are provided for short-term storage with limited memory capacity and fast access. A memory capacity that is multiples higher, but with diminished performance, is available in a following memory level. Jukeboxes with optical disks as storage media, file servers with tape systems, etc., are usually utilized for the on-line access.
It has proven advantageous in a such an-image system when the control unit, given outage of one of the memory systems, automatically causes subsequent data to be stored in one of the other memory systems or image stores.
The control can be simplified when distributors are arranged between the memory systems and the image stores.
The control can be simplified further, and the data flow and the use of the memory systems improved, when the image datasets are additionally provided with control data. The system components are then able to control the data flow dependent on the system status autonomously and decentrally.
DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a conventional imaging system having a networked data bank system.
FIG. 2 shows the structure of an inventively controlled memory system for use an imaging system.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows the system architecture of a conventional medical imaging communication network as an example. The modalities 1 through 4 , which, for example, can include a CT unit 1 for computed tomography, an MR unit 2 for magnetic resonance imaging, a DSA unit 3 for digital subtraction angiography and an X-ray unit 4 for digital radiography as image-generating units, serve for the acquisition of medical images. Work stations 5 through 8 with which the acquired medical images can be processed and locally stored can be connected to the modalities 1 through 4 . For example, such a work station can be a very fast, small computer having one or more fast processors.
The work stations 5 through 8 are connected to an image communication network 9 for the distribution of the generated images and for communication. Thus, for example, the images generated in- the modalities 1 through 4 and the images further-processed in the work stations 5 through 8 can be deposited in a central image storage system, such as an image memory 10 , or can be forwarded to other work stations.
Further work stations (diagnostic consoles) 11 and 12 are connected to the image communication network 9 as diagnosis consoles that contain local image memories. The images that have been acquired and deposited in the image memory 10 can be subsequently retrieved for diagnosis in the work stations 11 and 12 and are then deposited in the work station's local image memory, from which they can be immediately available to the diagnostician working at the work station 11 or 12 .
The image and data exchange via the image communication network 9 can ensue according to the DICOM standard, an industrial standard for the transmission of images and other medical information between computers for enabling digital communication between diagnostic and therapy apparatuses of different manufacturers. A network interface 13 , via which the internal. image communication network 9 is connected to a global data network, can be connected to the image communication network 9 , so that the standardized data can be exchanged world-wide with different networks.
FIG. 2 shows the memory structure of an inventive imaging system in detail. In addition to the work stations 11 and 12 , a patient data server 14 is connected to the image communication network 9 . The patient data server 14 serves the purpose of storing the image data flow. Additionally, those memory systems and memory levels in which the appertaining image datasets are deposited are known system-wide on the basis of the patient data and control data.
File servers 18 through 21 are connected to memory systems (distributors) 15 and 16 and are also connected to a number of jukeboxes 22 through 25 serving as image memories.
The patient data server 14 and the image data communication components of the work stations 11 and 12 and distributors 15 and 16 control the storage of the image datasets such that these datasets—independently of the sender—are routed in alternation into the distributors 15 and 16 connected to the image communication network 9 and their following memory levels, for example the file servers 18 through 21 , the jukeboxes 22 through 25 or other memory peripheries. Appropriately timed enablement of the various components to transmit or receive data is accomplished via control line 17 . The patient data server 14 also performs the function of causing these image datasets to be relocated only via the patient data, regardless of where they are stored. A balanced load when writing as well as when reading the image data in large systems as well as in small systems is achieved as a result of this new archiving principle of distributing the data stream over a number of memory systems and memory levels.
Given outage of individual memory elements, the others automatically assume their task.
Although modifications and changes may be suggested by those skilled in the art, it is the intention of the inventor to embody within the patent warranted hereon all changes and modifications as reasonably and properly come within the scope of his contribution to the art.
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A medical imaging system has a modality for acquiring images, components for processing the images, a communication linkage for the transmission of the images and memory arrangement for storing the images with a number of separate memory systems. The memory arrangement includes a control system which causes successive image datasets to be stored in separate memory systems.
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FIELD OF THE INVENTION
[0001] The invention relates to a method for improving the operation safety of the smelt spout area of a recovery boiler and the smelt spout area of a recovery boiler.
BACKGROUND OF THE INVENTION
[0002] The spent lye, i.e. the so-called black liquor created in pulp manufacture is burnt in a recovery boiler, on one hand, in order to recover the energy it includes, and on the other hand, in order to recover the chemicals in it and to recycle them back to circulation. A char bed is created on the bottom of the recovery boiler when burning black liquor, which in a high temperature forms into smelt, which is removed from the boiler as a continuous flow via smelt spouts to a dissolving tank.
[0003] Below the furnace is located the cover area of the dissolving tank of the recovery boiler, i.e. the smelt spout area, where the smelt from the lower part of the furnace is directed along the so-called smelt spout to the dissolving tank. FIG. 1 shows a typical smelt spout area of a recovery boiler, which comprises smelt spouts 2 , along which the smelt is directed from the furnace 3 to the dissolving tank 4 .
[0004] It is necessary to work in the vicinity of the smelt spouts relatively often, because the operation of the smelt spouts must be monitored at regular intervals. When necessary, pluggings must be removed from the smelt spouts in order for the smelt to be able to travel to the dissolving tank. In addition, the primary air nozzles 5 are often located in the vicinity of the smelt spout area (on the so-called primary register level), in which case checking and adjusting the nozzles requires working in the smelt spout area.
[0005] Typically, the smelt is very hot (for example 750 to 820° C.). The possible splashes of smelt cause danger to the personnel working and moving in the vicinity. Because of this, there is typically a protection area near the smelt spouts, moving on which area should be avoided and working on which area requires using special protection equipment.
SUMMARY OF THE INVENTION
[0006] The main purpose of the present invention is to disclose a new solution for increasing work safety.
[0007] To attain this purpose, the method according to the invention is primarily characterized in that in the method the smelt spouts are separated from the working area by a shielding wall arranged movable in relation to the smelt spouts. The smelt spout area of a recovery boiler according to the invention, in turn, is primarily characterized in that the smelt spout area comprises one or more shielding walls arranged movable in relation to the smelt spout in order to separate the smelt spouts from the working area. The dependent claims will present some preferred embodiments of the invention.
[0008] The basic idea of the invention is to arrange a shielding wall in front of the smelt spouts, which can be moved, for example closed and opened. According to the basic idea the closed shielding wall settles between the person working in the working area and the smelt spout. The shielding wall prevents the possible smelt splashes from falling on the person. In an advantageous embodiment the shielding wall also muffles the noise from the smelt spouts towards the working area. In an embodiment the heat radiation radiated from the smelt spouts to the working area is dampened by the shielding wall.
[0009] The method according to the invention discloses a solution for improving the operation safety of the smelt spout area of a recovery boiler, which smelt spout area comprises a working area, as well as smelt spouts connected to the lower part of the boiler to direct the smelt from the boiler to a dissolving tank. In the method, the smelt spouts are separated from the working area by a shielding wall that is arranged movable in relation to the smelt spouts. Correspondingly, in a power plant according to the invention, the smelt spout area comprises one or more shielding walls arranged movable in relation to the smelt spout in order to separate the smelt spouts from the working area.
[0010] In an embodiment the shielding wall is formed of one or more shielding units arranged movable. The shielding units can move in different directions application-specifically, such as, for example horizontally or vertically.
[0011] The movable shielding wall enables different usage, service and maintenance operations requiring a great deal of moving space. In an advantageous embodiment the shielding wall can be opened for a large uniform length.
[0012] The shielding wall can be implemented in a variety of ways. Advantageously the wall is formed of several units, in which case handling it is easier than handling large units. For example, the wall may be composed of sliding doors, lattice doors, shutters and/or folding doors. The direction of motion of individual units of the wall depends on the application. For example, the direction of motion can be horizontal or vertical. The wall can also move parallel or perpendicularly in relation to the bank of smelt spouts of the boiler.
[0013] In an embodiment the smelt spout area also comprises a service platform arranged movable in relation to the smelt spouts, which platform comprises a shielding wall. The service platform is meant for the usage, service and maintenance operations of targets located higher, such as the primary register level.
[0014] The shielding wall advantageously comprises inspection openings, such as, for example, windows and/or hatches that can be opened, through which it is possible to perform, inter alia, visual monitoring, rodding the spouts, as well as other usage, service and maintenance operation. There can be different kinds and shapes of hatches and windows, which provide as optimal as possible user interfaces for different tasks.
[0015] By the solution according to the invention, many significant advantages are achieved when compared with the solutions of prior art. The safety of the smelt spout area of a recovery boiler is improved, when the shielding structure separates the smelt spouts from the personnel. The shielding structure can application-specifically prevent different splashes, steams and/or pressure shocks from reaching the working area.
[0016] In an application the noise level of the smelt spout area is decreased. Muffling the noise is affected by the design and materials of the shielding structure. Decreased noise level improves work conditions and increases work safety for its part.
[0017] In one case the invention, in turn, enables the efficient utilization of the smelt spout area, because the shielding area can be decreased due to the shielding solution and the area that is thus freed can be used efficiently.
DESCRIPTION OF THE DRAWINGS
[0018] In the following, the invention will be described in more detail with reference to the appended principle drawings, in which
[0019] FIG. 1 shows a smelt spout area according to prior art,
[0020] FIG. 2 shows a side view of a smelt spout area according to the invention,
[0021] FIG. 3 shows a front view of a shielding wall unit according to the invention,
[0022] FIG. 4 shows a front view of a shielding wall according to the invention,
[0023] FIG. 5 shows the shielding wall of FIG. 4 along line A-A.
[0024] For the sake of clarity, the figures only show the details necessary for understanding the invention. The structures and details that are not necessary for understanding the invention, but are obvious for anyone skilled in the art, have been omitted from the figures in order to emphasize the characteristics of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0025] FIG. 1 shows a present smelt spout area of a recovery boiler. The area comprises smelt spouts 2 , along which the smelt is directed from the furnace 3 to the dissolving tank 4 . Generally in boilers the air nozzles 5 of the primary air level are placed above the smelt spouts 2 in such a manner that they can be accessed from the smelt spout area, for example, by means of some platform.
[0026] FIG. 2 shows the shielding wall 8 according to the invention in a side view. This direction is the same as the direction of the bank of smelt spouts 2 , i.e. the direction of the wall of the boiler. The shielding wall 8 is arranged between the working area 6 and the smelt spouts 2 . The working area 6 refers to that area of the smelt spout area, where the personnel works when performing usage, service and maintenance operation. In the case according to FIG. 2 , the working area 6 is the area to the left of the shielding wall 8 . In FIG. 2 , inter alia, a service platform 7 is located in the working area 6 , which platform forms its own, smaller working area. As can be seen in FIG. 2 , the shielding wall 8 protects the person 1 on the working area 6 by separating the person from a direct contact with the smelt spout 2 .
[0027] FIG. 3 shows a shielding unit 9 (shielding module, shielding element) forming the shielding wall 8 in a front view, i.e. when the viewing direction is from the working area 6 towards the smelt spouts 2 . In the example, the shielding unit 9 of the shielding wall 8 comprises two windows 11 , 12 . In the example, the upper one 11 of these windows is fixed and it is intended for performing visual monitoring. The lower window 12 can be opened and closed, and it enables performing the often repeated usage, service and maintenance operation, such as rodding, without having to move the shielding wall 8 to the side. Thanks to the windows 11 , 12 the shielding wall 8 does not need to be opened for visual inspection. Thus, the inspection can be performed from a protected space. There may be several hatches and/or windows 11 , 12 in the shielding wall 8 , or not necessarily any windows and/or hatches at all. The hatches can comprise windows or be solid, depending on the target of use. For example, the shielding wall 8 may comprise a hatch for working and a window for camera monitoring.
[0028] FIG. 4 shows an application, where the shielding wall 8 comprises several adjacent shielding units 9 shown in FIG. 3 . The shielding wall 8 can comprise one or more shielding units 9 . In the example, the shielding units 9 of the shielding wall 8 are certain kind of sliding doors, which can be slid in the direction of the boiler wall. For this purpose there are slide rails 13 at the bottom and top, which enable the sliding. Advantageously there are several adjacent rails 13 , such as, for example, three or four rails, in which case when opening the wall it is possible to slide several doors adjacently into a bundle and thus form a larger opening. This has been aimed to be illustrated in FIG. 5 , which shows the application of FIG. 4 in a top view along line A-A.
[0029] By opening the shielding wall 8 partly or entirely is created a large and as clear as possible passage to the area behind the line formed by the shielding wall 8 , such as, for example, to the smelt spouts 2 . Thus, it is easier to perform more extensive usage, service and maintenance operation. As can be seen in FIG. 5 , the opening of the shielding wall 8 can be performed by moving the shielding units 9 along the rails 13 . The shielding units 9 on different rails 13 can be mutually placed in such a manner that the second shielding unit is located behind the first shielding unit. The details connected to opening and closing the shielding wall 8 naturally depend on the structure of the shielding wall. The opening and closing may, for example, be based on overlapping, folding and/or removing.
[0030] In an application the attachment of the shielding unit 9 of the shielding wall 8 is arranged with a quick clamping, which enables the easy and fast detachment, and if necessary, the removal and/or changing of the shielding unit.
[0031] The shielding wall 8 may application-specifically be located on different sides of the boiler (on one or more sides). In a power plant application the shielding wall 8 is on those sides of the boiler where the smelt spouts 2 are located. In another power plant application the shielding wall 8 is placed around the boiler.
[0032] The structure of the shielding wall 8 and the individual shielding units 9 may vary application-specifically. Some possible solutions include different kinds of sliding doors, lattice doors, folding doors, roller shutters, etc. In addition, the direction of motion of the shielding units 9 may vary application-specifically. In the previous example the direction of motion of the shielding units 9 is horizontal and in the direction of the boiler wall. In another application the direction of motion of the shielding unit 9 is substantially perpendicular to the boiler wall. In an application the direction of motion of the shielding unit 9 is substantially vertical. In an application the direction of motion of the movement taking place vertically is, in turn, slanted. Especially different curtain-type shielding walls 8 are advantageous to be arranged to move upwards, preferably vertically if possible, in which case the structure does not necessarily have to be rigid in order to control the movement of the shielding wall 8 . The movement of the shielding wall 8 can also be controlled by different solutions, such as, for example, rolls, glides, guide bars, hinges and junction structures.
[0033] In selecting the material for the shielding wall 8 it is advantageous to pay attention to, inter alia, thermal resistance and the resistance of the occurring chemicals. The shielding wall 8 should be incombustible and preferably sound-insulating. Because of ease of processing the shielding units 9 of the shielding wall 8 should be light, which, in addition to the materials, is affected by the size and shape of the shielding unit. In some tests a shielding wall 8 manufactured of stainless steel has been detected to be useful. Its sound-insulation can be improved with different sound-insulating materials. There are also other alternatives, such as, for example structures manufacture entirely or partly of metal, composite or ceramic.
[0034] The shielding wall 8 must also endure great temperature fluctuations, which occur, inter alia, in connection with the start-up and shutdown of the boiler. Thermal radiation of the boiler causes the dimensions of the shielding wall 8 to change. In addition, a change in the temperature of the shielding wall 8 causes the dimensions to change in its structure. For easy handling the shielding wall 8 must enable the thermal expansion of both the shielding wall and other structures. The changes caused by thermal expansion affecting the shielding wall 8 may be several tens of centimeters in size. The shielding wall 8 can, for example, be implemented in such a manner that its structure is flexible or its structure increases and decreases according to need. It is also possible that the attachment solution enables thermal radiation.
[0035] The space around the boiler defined by the shielding wall can be substantially solid or breathing. A breathing structure can be implemented in a variety of ways. The shielding wall 8 can, for example, be formed in such a manner that air can flow between the shielding units 9 of the shielding wall. It is also possible to use different breather and valve structures for pressure balancing. The flow of air and other gases can also be controlled with various types of channel structures. For example, a pipe can be lead to the outside from the space defined around the boiler by the shielding wall 8 . Different pressure shocks may occur in the space in question, for example, when a malfunction is created in the smelt spout 2 , such as, for example, a smelt flush.
[0036] FIGS. 2 and 4 show a service platform 7 as well. In the example, the service platform 7 is intended for the usage, service and maintenance operation of the so-called primary register level. In the example according to the figure, the primary register level is above the smelt spouts 2 and it comprises, inter alia, primary air nozzles 5 . The service platform 7 is arranged to be movable. In the example, the service platform 7 comprises wheels, which are located in the rails 14 in the floor. The path of the service platform 7 is controlled by means of the rails 14 . It is also possible to arrange the service platform 7 to be movable in another manner. Moving the service platform 7 and/or the shielding wall 8 may application-specifically take place either manually and/or with engine power, such as, for example, by electric motor usage.
[0037] The shielding wall 8 described above protects the person 1 on the service platform 7 . It is also possible to arrange a shielding wall 10 in connection with the service platform 7 . Thus, the shielding wall 10 moves along with the service platform 7 always being between the working area of the service platform and the smelt spouts 2 , thus protecting the working area. The shielding wall 10 of this service platform 7 can also be equipped with different hatches and windows, for example, as has been described above. The size and appearance of the shielding wall 10 of the service platform may vary depending on the target of use.
[0038] The shielding effect of the shielding wall 8 , as well as work safety can be improved by arranging the devices in the smelt spout area in advantageous positions. By designing the primary air nozzles 5 for example smaller, the working position is made safer and more ergonomic. As can be seen in FIG. 2 , by arranging the first side of the air nozzle 5 (the side opposite to the side connected to the furnace) close to the vertical line formed by the shielding wall 8 , the person 1 does not have to reach as much as in solutions of prior art.
[0039] By combining, in various ways, the modes and structures disclosed in connection with the different embodiments of the invention presented above, it is possible to produce various embodiments of the invention in accordance with the spirit of the invention. Therefore, the above-presented examples must not be interpreted as restrictive to the invention, but the embodiments of the invention may be freely varied within the scope of the inventive features presented in the claims hereinbelow.
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A method for improving the operation safety of the smelt spout area of a recovery boiler, which smelt spout area comprises a working area ( 6 ), as well as smelt spouts ( 2 ) connected to the lower part of the boiler for directing the smelt from the boiler to a dissolving tank ( 4 ). In the method the smelt spouts ( 2 ) are separated from the working area ( 6 ) by a shielding wall ( 8, 10 ) arranged movable in relation to the smelt spouts. The invention also relates to a smelt spout area of a recovery boiler.
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BACKGROUND OF THE INVENTION
This invention relates to a heat source which is particularly useful in smoking articles. More particularly, this invention relates to metal carbide heat sources which, upon combustion, produce substantially no carbon monoxide. The metal carbide particles making up the heat sources of this invention have ignition temperatures that are substantially lower than conventional carbon particles normally used in carbonaceous heat sources, while at the same time provide sufficient heat to release a flavored aerosol from a flavor bed for inhalation by the smoker. This invention is particularly suitable for use in a smoking article such as that described in copending U.S. patent application Ser. No. 223,153, filed on July 22, 1988.
There have been previous attempts Lo provide a heat source for a smoking article. While providing a heat source, these attempts have not produced a heat source having all of the advantages of the present invention.
For example, Siegel U.S. Pat. No. 2,907,686 discloses a charcoal rod coated with a concentrated sugar solution which forms an impervious layer during burning. It was thought that this layer would contain gases formed during smoking and concentrate the heat thus formed.
Ellis et al. U.S. Pat. No. 3,258,015 and Ellis et al. U.S. Pat. No. 3,356,094 disclose a smoking device comprising a nicotine source and a tobacco heat source.
Boyd et al. U.S. Pat. No. 3,943,941 discloses a tobacco substitute which consists of a fuel and at least one volatile substance impregnating the fuel. The fuel consists essentially of combustible, flexible and self-coherent fibers made of a carbonaceous material containing at least 80% carbon by weight. The carbon is the product of the controlled pyrolysis of a cellulose-based fiber containing only carbon, hydrogen and oxygen.
Bolt et al. U.S. Pat. No. 4,340,072 discloses an annular fuel rod extruded or molded from tobacco, a tobacco substitute, a mixture of tobacco substitute and carbon, other combustible materials such as wood pulp, straw and heat-treated cellulose or a sodium carboxymethylcellulose (SCMC) and carbon mixture.
Shelar et al. U.S. Pat. No. 4,708,151 discloses a pipe with replaceable cartridge having a carbonaceous fuel source. The fuel source comprises at least 60-70% carbon, and most preferably 80% or more carbon, and is made by pyrolysis or carbonization of cellulosic materials such as wood, cotton, rayon, tobacco, coconut, paper and the like.
Banerjee et al. U.S. Pat. No. 4,714,082 discloses a combustible fuel element having a density greater than 0.5 g/cc. The fuel element consists of comminuted or reconstituted tobacco and/or a tobacco substitute, and preferably contains 20-40% by weight of carbon.
Published European patent application 0 117 355 by Hearn et al. discloses a carbon heat source formed from pyrolized tobacco or other carbonaceous material such as peanut shells, coffee bean shells, paper, cardboard, bamboo, or oak leaves.
Published European patent application 0 236 992 by Farrier et al. discloses a carbon fuel element and process for producing the carbon fuel element. The carbon fuel element contains carbon powder, a binder and other additional ingredients, and consists of between 60 and 70% by weight of carbon.
Published European patent application 0 245 732 by White et al. discloses a dual burn rate carbonaceous fuel element which utilizes a fast burning segment and a slow burning segment containing carbon materials of varying density.
These heat sources are deficient because they provide unsatisfactory heat transfer to the flavor bed, resulting in an unsatisfactory smoking article, i.e., one which fails to simulate the flavor, feel and number of puffs of a conventional cigarette.
Copending U.S. patent application Ser. No. 223,232, filed on July 22, 1988, solved this problem by providing a carbonaceous heat source formed from charcoal that maximizes heat transfer to the flavor bed, releasing a flavored aerosol from the flavor bed for inhalation by the smoker, while minimizing the amount of carbon monoxide produced.
However, all conventional carbonaceous heat sources liberate some amount of carbon monoxide gas upon ignition. Moreover, the carbon contained in these heat sources has a relatively high ignition temperature, making ignition of conventional carbonaceous heat sources difficult under normal lighting conditions for a conventional cigarette.
Attempts have been made to produce non-combustible heat sources for smoking articles, in which heat is generated electrically. E.g., Burruss, Jr., U.S. Pat. No. 4,303,083, Burruss U.S. Pat. No. 4,141,369, Gilbert U.S. Pat. No. 3,200,819, McCormick U.S. Pat. No. 2,104,266 and Wyss et al. U.S. Pat. No. 1,771,366. These devices are impractical and none has met with any commercial success.
It would be desirable to provide a heat source that liberates virtually no carbon monoxide upon combustion.
It would also be desirable to provide a heat source that has a low temperature of ignition to allow for easy lighting under conditions typical for a conventional cigarette, while at the same time providing sufficient heat to release flavors from a flavor bed.
It would further be desirable to provide a heat source that does not self-extinguish prematurely.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a heat source that liberates virtually no carbon monoxide gas upon combustion.
It is also an object of this invention to provide a heat source that has an ignition temperature lower than that of conventional heat sources.
It is yet another object of this invention to provide a heat source that does not self-extinguish prematurely.
In accordance with this invention, there is provided a heat source, which is particularly useful in a smoking article. The heat source is formed from materials having a substantial metal carbide content, particularly an iron carbide, and more particularly an iron carbide having the formula Fe x C, where x is between 2 and 3. The heat source may have one or more longitudinal passageways, as described in copending U.S. patent application Ser. No. 223,232, filed on July 22, 1988, or may have one or more grooves around the circumference of the heat source such that air flows along the outside of the heat source. Alternatively, the heat source could be formed with a porosity sufficient to allow heat flow through the heat source. When the heat source is ignited and air is drawn through the smoking article, the air is heated as it passes around or through the heat source or through, over or around the air flow passageways or grooves. The heated air flows through a flavor bed, releasing a flavored aerosol for inhalation by the smoker.
Metal carbides are hard, brittle materials, which are readily reducible to powder form. Iron carbides consist of at least two well-characterized phases--Fe 5 C 2 , also known as Hagg's compound, and Fe 3 C, referred to as cementite. The iron carbides are highly stable, interstitial crystalline molecules and are ferromagnetic at room temperature. Fe 5 C 2 has a reported monoclinic crystal structure with cell dimensions of 11.56 angstroms by 4.57 angstroms by 5.06 angstroms. The angle β is 97.8 degrees. There are four molecules of Fe 5 C 2 per unit cell. Fe 3 C is orthorhombic with cell dimensions of 4.52 angstroms by 5.09 angstroms by 6.74 angstroms. Fe 5 C 2 has a Curie temperature of about 248 degrees centigrade. The Curie temperature of Fe 3 C is reported to be about 214 degrees centigrade. J. P. Senateur, Ann. Chem., vol. 2, p. 103 (1967).
Upon combustion, the metal carbides of the heat source of this invention liberate substantially no carbon monoxide. While not wishing to be bound by theory, it is believed that essentially complete combustion of the metal carbide produces metal oxide and carbon dioxide, without production of any significant amount of carbon monoxide.
In a preferred embodiment of this invention, the heat source comprises iron carbide, preferably rich in carbides having the formula Fe 5 C 2 . Other metal carbides suitable for use as a heat source in this invention are carbides of aluminum, titanium, manganese, tungsten and niobium, or mixtures thereof. Catalysts and oxidizers may be added to the metal carbide to promote complete combustion and to provide other desired burn characteristics.
While the metal carbide heat sources of this invention are particularly useful in smoking devices, it is to be understood that they are also useful as heat sources for other applications, where having the characteristics described herein are desired.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects and advantages of this invention will be apparent upon consideration of the following detailed description, taken in conjunction with the accompanying drawings, in which like reference characters refer to like parts throughout, and in which:
FIG. 1 depicts an end view of one embodiment of the heat source of this invention; and
FIG. 2 depicts a longitudinal cross-sectional view of a smoking article in which the heat source of this invention may be used.
DETAILED DESCRIPTION OF THE INVENTION
Smoking article 10 consists of an active element 11, an expansion chamber tube 12, and a mouthpiece element 13, overwrapped by a cigarette wrapping paper 14. Active element 11 includes a metal carbide heat source 20 and a flavor bed 21 which releases flavored vapors when contacted by hot gases flowing through heat source 20. The vapors pass into expansion chamber tube 12, forming an aerosol that passes to mouthpiece element 13, and then into the mouth of a smoker.
Heat source 20 should meet a number of requirements in order for smoking article 10 to perform satisfactorily. It should be small enough to fit inside smoking article 10 and still burn hot enough to ensure that the gases flowing therethrough are heated sufficiently to release enough flavor from flavor bed 21 to provide flavor to the smoker. Heat source 20 should also be capable of burning with a limited amount of air until the metal carbide in the heat source is expended. Upon combustion, heat source 20 should produce virtually no carbon monoxide gas.
Heat source 20 should have an appropriate thermal conductivity. If too much heat is conducted away from the burning zone to other parts of the heat source, combustion at that point will cease when the temperature drops below the extinguishment temperature of the heat source, resulting in a smoking article which is difficult to light and which, after lighting, is subject to premature self-extinguishment. Such extinguishment is also prevented by having a heat source that undergoes essentially 100% combustion. The thermal conductivity should be at a level that allows heat source 20, upon combustion, to transfer heat to the air flowing through it without conducting heat to mounting structure 24. Oxygen coming into contact with the burning heat source will almost completely oxidize the heat source, limiting oxygen release back into expansion chamber tube 12. Mounting structure 24 should retard oxygen from reaching the rear portion of the heat source 20, thereby helping to extinguish the heat source after the flavor bed has been consumed. This also prevents the heat source from falling out of the end of the smoking article.
Finally, ease of lighting is also accomplished by having a heat source with an ignition temperature sufficiently low to permit easy lighting under normal conditions for a conventional cigarette.
The metal carbides of this invention generally have a density of between 2 and 10 gr/cc and an energy output of between 1 and 10 kcal/gr., resulting in a heat output of between 2 and 20 kcal/cc. This is comparable to the heat output of conventional carbonaceous materials. These metal carbides undergo essentially 100% combustion, producing only metal oxide and carbon dioxide gas, with substantially no liberation of carbon monoxide gas. They have ignition temperatures of between room temperature and 550 degrees centigrade, depending on the chemical composition, particle size, surface area and Pilling Bedworth ratio of the metal carbide.
Thus, the preferred metal carbides for use in the heat source of this invention are substantially easier to light than conventional carbonaceous heat sources and less likely to self-extinguish, but at the same time can be made to smolder at lower temperatures.
The rate of combustion of the heat source made from metal carbides can be controlled by controlling the particle size, surface area and porosity of the heat source material and by adding certain materials to the heat source. These parameters can be varied to minimize the occurrence of side reactions in which free carbon may be produced and thereby minimize production of carbon monoxide that may form by reaction of the free carbon with oxygen during combustion. Such methods are well-known in the art.
For example, the metal carbide in heat source 20 may be in the form of small particles. Varying the particle size will have an effect on the rate of combustion. The smaller the particles are, the more reactive they become because of the greater availability of surface to react with oxygen for combustion. This results in a more efficient combustion reaction. The size of these particles can be up to about 700 microns. Preferably the metal carbide particles have an average particle size of about submicron to about 300 microns. The heat source may be synthesized at the desired particle size, or, alternatively, synthesized at a larger size and ground down to the desired size.
The B.E.T. surface area of the metal carbide also has an effect on the reaction rate. The higher the surface area, the more rapid the combustion reaction. The B.E.T. surface area of heat source 20 made from metal carbides should be between 1 and 400 m 2 /gr, preferably between about 10 and 200 m 2 /gr.
Increasing the void volume of the metal carbide particles will increase the amount of oxygen available for the combustion reaction, thereby increasing the reaction rate. Preferably, the void volume is from about 25% to about 75% of the theoretical maximum density.
Heat loss to the surrounding wrapper 14 of smoking article 10 may be minimized by insuring that an annular air space is provided around heat source 20. Preferably heat source 20 has a diameter of about 4.6 mm and a length of 10 mm. The 4.6 mm diameter allows an annular air space around the heat source without causing the diameter of the smoking article to be larger than that of a conventional cigarette.
In order to maximize the transfer of heat from the heat source to flavor bed 21, one or more air flow passageways 22 may be formed through or along the circumference of heat source 20. The air flow passageways should have a large geometric surface area to improve the heat transfer to the air flowing through the heat source. The shape and number of the passageways should be chosen to maximize the internal geometric surface area of heat source 20. Preferably, when longitudinal air flow passageways such as those depicted in FIG. 1 are used, maximization of heat transfer to the flavor bed is accomplished by forming each longitudinal air flow passageway 22 in the shape of a multi-pointed star. Even more preferably, as set forth in FIG. 1, each multi-pointed star should have long narrow points and a small inside circumference defined by the innermost edges of the star. These star-shaped longitudinal air flow passageways provide a larger area of heat source 20 available for combustion, resulting in a greater volume of metal carbide involved in combustion, and therefore a hotter burning heat source.
A certain minimum amount of metal carbide is needed in order for smoking article 10 to provide a similar amount of static burn time and number of puffs to the smoker as a conventional cigarette. Typically, the amount of heat source 20 that is converted to metal oxide is about 50% of the volume of a heat source cylinder that is 10 mm long by 4.65 mm in diameter. A greater amount may be needed taking into account the volume of heat source 20 surrounded by and in front of mounting structure 24 which, as discussed above, is not combusted.
Heat source 20 should have a density of from about 25% to about 75% of the theoretical maximum density of the metal carbide. Preferably, the density should be between about 30% and about 60% of its theoretical maximum density. The optimum density maximizes both the amount of carbide and the availability of oxygen at the point of combustion. If the density becomes too high the void volume of heat source 20 will be low. Lower void volume means that there is less oxygen available at the point of combustion. This results in a heat source that is harder to burn. However, if a catalyst is added to heat source 20, it is possible to use a dense heat source, i.e., a heat source with a small void volume having a density approaching 90% of its theoretical maximum density.
Certain additives may be used in heat source 20 to modify the smoldering characteristics of the heat source. This aid may take the form of promoting combustion of the heat source at a lower temperature or with lower concentrations of oxygen or both.
Heat source 20 can be manufactured by slip casting, extrusion, injection molding, die compaction or used as a contained, packed bed of small individual particles.
Any number of binders could be used to bind the metal carbide particles together when the heat source is made by extrusion or die compaction, for example sodium carboxymethylcellulose (SCMC). The SCMC may be used in combination with other additives such as sodium chloride, vermiculite, bentonite or calcium carbonate. Other binders useful for extrusion or die compaction of the metal carbide heat sources of this invention include gums, such as guar gum, other cellulose derivatives, such as methylcellulose and carboxymethylcellulose, hydroxypropyl cellulose, starches, alginates and polyvinyl alcohols.
Varying concentrations of binders can be used, but it is desirable to minimize the binder concentration to reduce the thermal conductivity and improve the burn characteristic of the heat source. It is also important to minimize the amount of binder used to the extent that combustion of the binder may liberate free carbon which could then react with oxygen to form carbon monoxide.
The metal carbide used to make heat source 20 is preferably iron carbide. A suitable iron carbide has the formula Fe 5 C 2 . Other useful iron carbides have the formula Fe 3 C, Fe 4 C, Fe 7 C 2 , Fe 9 C 4 and Fe 20 C 9 , or mixtures thereof. These mixtures may contain a small amount of carbon. The ratio of iron molecules to carbon molecules in the iron carbide will affect the ignition temperature of the iron carbide.
Other metal carbides suitable for use in the heat source of this invention include carbides of aluminum, titanium, tungsten, manganese and niobium, or mixtures thereof.
Preparation Of Iron Carbide
Iron carbide was synthesized using a variation of the method disclosed in J. P. Senateur, Ann. Chem., vol. 2, p. 103 (1967). That method involved the reduction and carburization of high surface area reactive iron oxide (Fe 2 O 3 ) using a mixture of hydrogen and carbon monoxide gases. Methods such as thermal degradation of iron oxylate or iron citrate are well-known. P. Courty and B. Delmon, C.R. Acad. Sci. Paris Ser. C., vol. 268, pp. 1874-75 (1969). The particular iron carbide prepared depends on the temperature of the reaction mixture and the ratio of the hydrogen and carbon monoxide gases. Reaction temperatures of between 300 and 350 degrees centigrade yield Fe 5 C 2 , whereas primarily Fe 3 C will be produced at temperatures greater that 350 degrees centigrade. The ratio of hydrogen to carbon monoxide can be varied from 0:1 to 10:1, depending on the temperature. This ratio was controlled using two separate flowmeters connected to each gas source. The combined flow was 70 standard cubic centimeters per minute.
1. Synthesis of Fe 5 C 2
High surface area iron oxide was prepared by heating iron nitrate (Fe(NO 3 ) 3 9H 2 O) in air at 400 degrees centigrade. The iron oxide was then carburized by placing it in a furnace at 300 degrees centigrade under flowing hydrogen-carbon monoxide gas mixture at a ratio of 7 to 1 for twelve hours to produce the iron carbide. If desired, a hydrogen-methane gas mixture can be used in place of the hydrogen-carbon monoxide gas mixture. The iron oxide sample had an X-ray powder diffraction pattern indicative of Fe 5 C 2 , as compared to the JCPDS X-Ray Powder Diffraction File. The sample was grayish-black in color.
2. Synthesis of Fe 3 C
This sample was prepared using similar procedures to those described for production of Fe 5 C 2 , except that the iron oxide was carburized at 500 degrees centigrade. X-ray powder diffraction analyses confirmed that primarily Fe 3 C was produced.
3. Analyses of Iron Carbides
We determined the B.E.T. surface area (using nitrogen gas), ignition temperature and heat of combustion of the iron carbides produced by the above methods. The results were as follows:
______________________________________B.E.T. Surface Ignition Heat OfArea Temperature Combustion______________________________________Fe.sub.5 C.sub.2 26 m.sup.2 /gr 155° C. 2400-2458 Cal/grFe.sub.3 C 20 m.sup.2 /gr 380° C. --______________________________________
Gas phase analyses indicated that the CO 2 /CO gas ratio was 30:1 by weight for Fe 5 C 2 , whereas the ratio for carbon is 3:1 by weight. Thus 10 times less carbon monoxide is produced upon combustion of the Fe 5 C 2 sample than of carbon.
Thus, it is seen that this invention provides a metal carbide heat source that forms virtually no carbon monoxide gas upon combustion and has a significantly lower ignition temperature than conventional carbonaceous heat sources, while at the same time maximizes heat transfer to the flavor bed. One skilled in the art will appreciate that the present invention can be practiced by other than the described embodiments, which are presented herein for the purpose of illustration and not of limitation, and that the present invention is limited only by the claims which follow.
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An iron carbide heat source, particularly useful in smoking articles, is provided. The iron carbide particles making up the heat source have ignition temperatures that are substantially lower than conventional carbon particles normally used in carbonaceous heat sources, while at the same time provide sufficient heat to release a flavored aerosol from a flavor bed for inhalation by the smoker. In a preferred embodiment, the iron carbide heat source of this invention is substantially cylindrical in shape and has one or more fluid passages therethrough. Upon combustion, the heat source produces substantially no carbon monoxide.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Priority to U.S. Provisional Application No. 60/440,275, filed Jan. 15, 2003 and hereby incorporated by reference herein, is claimed.
BACKGROUND OF THE INVENTION
[0002] The present invention relates generally to printed materials and more particularly to trimming units for trimming edges of a book.
[0003] U.S. application No. 2002/0034428 discloses a trimmer for trimming excess margins along one, two or three edges of a perfect bound book. The book is gripped by a book holder, and a shearing blade cuts the edges of the book. The shearing blade has a flat edge and reciprocates.
[0004] European Patent Application No. 1 201 379 discloses a three-sided trimmer having a top edge cutting knife, a bottom edge cutting knife and a fore edge cutting knife, all with flat edges and reciprocating.
[0005] European Patent Application No. 0 893 277 discloses a trimmer, particularly for trimming book backs. A milling cutter has a disc-shaped body specially shaped teeth. The trimmer is a rotary cutter.
[0006] A problem associated with prior art trimmers used for trimming books is the delamination of the cover of a book from the interior sheet material, or the tearing of the book material. This trim defect is typically called “chipout” or “tearout”.
[0007] It has been known to score the spine of the book with scoring knives before the head and foot of the book are trimmed.
SUMMARY OF THE INVENTION
[0008] Co-pending U.S. application Ser. No. 10/208,551 of the present assignee, filed Jul. 20, 2002 and hereby incorporated by reference herein, discloses a trimming blade for minimizing chipout.
[0009] Mechanical scoring knives face issues such as blade wear, cycling times and problems scoring shapes.
[0010] An object of the present invention is to improve the trimming of books, especially of the sides of books adjacent to the spine. Another alternate or additional object of the present invention is to reduce chipout. Yet another alternate or additional object of the present invention is to improve scoring speed and/or provide for scoring of irregularly shaped spines and/or improve wear characteristics of a scoring device.
[0011] The present invention provides a trimmer for trimming a book comprising:
[0012] a support for supporting a book;
[0013] at least one laser for scoring an edge of the book so as to produce a score; and
[0014] a trimming station for trimming the book at the score.
[0015] By using a laser to produce a score, chipout may be minimized. Scoring speed and scoring device wear can be improved. Irregularly shaped edges can be scored.
[0016] Preferably, the edge is a spine of the book. The laser may score, for example, an outer layer of cover material at the spine or through the entire spine.
[0017] The support preferably is a conveyor and the at least one laser is stationary.
[0018] Advantageously, two lasers may be used to score the edge at the head and the foot of the book, although one laser also may be used. A single laser with a beam splitter may also be used.
[0019] The laser beam of the laser preferably contacts the edge at an acute angle, although other angles may be used.
[0020] The trimmer may be a three-edge trimmer, with a face trimming station and with a head and foot trimming station as the trimming station for trimming at the score. Preferably, the laser scoring device scores the spine just upstream of the head and foot station. For example, in certain trimmers the laser scoring device may be downstream from the face trimming station, so that the action of the face trimming station does not alter the score location for the head and foot station.
[0021] The present invention also provides a method for trimming a book comprising the steps of scoring an edge of the book using a laser so as to create a score, and trimming the book at the score.
[0022] Also provided is a laser scoring station comprising a support for supporting a book and at least one laser for scoring an edge of the book so as to produce a score.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] [0023]FIG. 1 shows one embodiment of the trimmer of the present invention using two lasers.
DETAILED DESCRIPTION
[0024] [0024]FIG. 1 shows an embodiment of a trimmer for books 30 A, 30 B, 30 C, 30 D moving in a direction 22 . The books have their spines facing forward, so that for example spine 32 A of book 30 A faces in the direction of travel. A first conveyor 12 moves book 30 A to a face trimming station 10 having a reciprocating blade 14 for trimming the face of the book 30 A. Retractable stops 21 may stop the spine 32 A to position the face for trimming. The face is opposite spine 32 A. Book 30 A may be clamped in face trimming station 10 during the face trimming operation.
[0025] The stops may then be retracted and the books are then transferred, for example by conveyor 12 , to conveyor 20 , which may have a lower and top belt to transport the books. At a spine scoring location 18 , book 30 B may be scored by lasers 40 , 42 at both a head location 34 and a foot location 36 . Lasers 40 , 42 thus are located at the sides of the conveyor 20 , and supported by a frame 50 . Lasers 40 , 42 may be adjustable with respect to the frame 50 for minor adjustments of the score position, but are fixed during operation. Lasers 40 , 42 may score the spine at an angle A, which may be for example 45 degrees.
[0026] A controller 70 may have an input identifying the position and speed of the products on conveyor 20 , and control the pulsing of the lasers 70 , 72 so that the laser beams of the lasers 70 , 72 score the laser for an appropriate amount of time at an appropriate power. A thickness of the book can also be input into controller 70 . The score preferably cuts through the spine, for example the glued section of the spine. Angle A preferably is an acute angle.
[0027] Scored book 30 C passes by the lasers 40 , 42 to a head and foot trimming station 60 , where a reciprocating head trimming blade 64 trims the head of book 30 D at a score location equivalent to score 34 and a reciprocating foot blade 62 trims the foot of the book 30 D at a score location equivalent to score 36 of book 30 B. The book 30 D may be clamped during the trimming operation of station 60 .
[0028] The laser scoring reduces chipout caused by the blades 62 , 64 . The laser scoring reduces scoring blade wear, and permits for faster scoring.
[0029] For many applications, the lasers 70 , 72 may be for example RF excited CO2 lasers from the firm Coherent, Inc. operating at a wavelength of 10.6 micrometers and having a power of 30 watts. Appropriate scores using such lasers for certain trimmers for book thicknesses up to 1 inch may result for example at conveyor speeds of about 50 meters per second and pulse times of about 0.3 seconds. However, other types of lasers may be used.
[0030] The present invention is not limited to any specific speeds, laser types, laser powers, pulse durations, trimmer blade types, trimmer types or book thicknesses, and the appropriate combination of such attributes may be determined as required by the specific application. For example, such attributes may be determined for a particular trimmer by viewing finished books for chipout, and altering one or more attribute to reduce chipout if chipout has occurred. Such attributes also may change depending on a type of glue used for the spine, for example. The attributes may also be changed upon a review by an operator of the scoring depth of the score. For example, if the score appears to be too shallow, the pulse duration or laser power may be increased.
[0031] While a specific trimmer has been disclosed, the trimmer may be of any type, including a single station trimmer that does not convey the book.
[0032] “Book” as defined herein may be any collection of sheet material with a spine.
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A trimmer for trimming a book has a support for supporting a book, at least one laser for scoring an edge of the book so as to produce a score, and a trimming station for trimming the book at the score.
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BACKGROUND OF THE INVENTION
[0001] Exemplary embodiments pertain to the art of motor vehicles and, more particularly, to an energy harvesting system for a motor vehicle.
[0002] Motor vehicles including land vehicles, water vehicles, and air vehicles include multiple electrical loads that are often powered by a battery. Oftentimes, the electrical loads are connected to the battery through long runs of electrical conductors or wires. As motor vehicles grow in complexity, the use of electrical components and, by extension, the need for more electrical conductors and connectors increases. The number of electrical conductors and connectors added to a motor vehicle represents a significant weight load that may impact performance. For example, the weight associated with the electrical conductors may have a negative impact on gas mileage for motor vehicles, or load maximums for air based vehicles. Also, the long runs of electrical conductors are exposed to harsh environments, including vibration, that could create open circuits that are hard to locate and repair.
BRIEF DESCRIPTION OF THE INVENTION
[0003] Disclosed is an energy harvesting system for an aircraft including an energy storage device, and an energy harvesting member electrically connected to the energy storage device and mechanically linked to the aircraft. The energy harvesting member is configured and disposed to generate an electrical energy output in response to one of a change in altitude of, or turbulence on, the aircraft.
[0004] Also disclosed is an aircraft including a body having an exterior surface and one or more interior surfaces, an energy storage device arranged in the body, and an energy harvesting member electrically connected to the energy storage device and mechanically linked to the body. The energy harvesting member is configured and disposed to generate an electrical energy output in response to one of a change in altitude of, or turbulence on, the body of the aircraft.
[0005] Still further disclosed is a method of harvesting electrical energy in an aircraft. The method includes exposing an energy harvesting member mounted to a surface of the aircraft to one of a change in altitude or turbulence, generating an electrical energy in the energy harvesting member in response to the one of the change in altitude or turbulence, passing the electrical energy from the energy harvesting member to an electrical storage device, and storing the electrical energy in the electrical storage device.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike:
[0007] FIG. 1 is a perspective view of an aircraft including an energy harvesting system, in accordance with an exemplary embodiment;
[0008] FIG. 2 is a schematic view of the energy harvesting system of FIG. 1 ;
[0009] FIG. 3 is a schematic view of an energy harvesting system, in accordance with another aspect of an exemplary embodiment; and
[0010] FIG. 4 is a schematic view of an energy harvesting system, in accordance with yet another aspect of the exemplary embodiment.
DETAILED DESCRIPTION OF THE INVENTION
[0011] A detailed description of one or more embodiments of the disclosed apparatus and method are presented herein by way of exemplification and not limitation with reference to the Figures.
[0012] An aircraft, in accordance with an exemplary embodiment, is indicated generally at 2 , in FIG. 1 . Aircraft 2 includes a body 4 having a forward or nose portion 6 and an aft or tail portion 8 . Tail portion 8 includes a vertical stabilizer 10 , a first horizontal stabilizer 12 , and a second horizontal stabilizer 14 . Aircraft 2 also includes a first wing 16 extending from a port side (not separately labeled) of body 4 and a second wing 18 extending from a starboard side (also not separately labeled) of body 4 . Body 4 includes an exterior or lower pressure surface 22 and an interior surface 24 ( FIG. 2 ). Interior surface 24 defines an area of high or steady pressure 26 and exterior surface 22 defines an area of lower or fluctuating pressure 28 .
[0013] In accordance with an exemplary embodiment, aircraft 2 includes an energy harvesting member 40 mounted to body 4 . In the exemplary aspect shown, energy harvesting member 40 may take the form of a pressure transducer 46 mounted to exterior surface 22 . Pressure transducer 46 is electrically coupled to an energy storage device 50 which may take the form of an ultracapacitor 52 . Energy storage device 50 may be electrically coupled to an electrical load 54 which may take the form of a light 56 , such as an LED. Of course it should be understood that one or more electrical control devices, such as a switch (not shown), may be electrically connected between energy harvesting member 40 and electrical storage device 50 ; and between electrical storage device 50 and electrical load 54 .
[0014] In accordance with an exemplary embodiment, aircraft 2 experiences variations in pressure between high pressure zone 26 and low pressure zone 28 during various points of flight. Pressure changes occur during changes in altitude both on ascent and decent, as well as during periods of turbulence. The pressure changes lead to pressure fluctuations that create a zone of fluctuating pressure 60 about pressure transducer 46 . The pressure fluctuations act upon pressure transducer 46 resulting in generation of an electrical current that is passed to energy storage device 50 . The energy may be used to power light 56 . In this manner, power may be provided for an electrical load without the need for long runs of conductors that increase complexity, manufacturing costs, and an overall weight of the aircraft. The number of energy harvesting devices may vary and can be located on any surface of body 4 .
[0015] Reference will now be made to FIG. 3 in describing an energy harvesting member 68 , in accordance with another aspect of the exemplary embodiment. Energy harvesting member 68 may take the form of a micro-turbine 70 provided in body 4 between exterior surface 22 and interior surface 24 . Micro-turbine 70 responds to flows of air currents by creating electrical energy. Micro-turbine 70 is operatively connected to an energy storage device 72 which may take the form of a battery 74 . Energy storage device 72 is electrically coupled to an electrical load 76 that may be a speaker or a Wi-Fi connection 78 .
[0016] During flight, and in particular during altitude changes, air is expressed from high pressure zone 26 to low pressure zone 28 . In accordance with the exemplary embodiment, at least a portion of the air is passed through one or more micro-turbines 70 to generate electrical energy for operating electrical load 76 . In this manner, power may be provided for an electrical load without the need for long runs of conductors that increase complexity, manufacturing costs and an overall weight of the aircraft. The number of energy harvesting devices may vary and can be located on any surface of body 4 .
[0017] Reference will now be made to FIG. 4 in describing an energy harvesting member 88 , in accordance with another aspect of the exemplary embodiment. Energy harvesting member 88 takes the form of a piezo-electric element 90 that is mounted to interior surface 24 . Of course it should be understood that piezo-electric element 90 may also be mounted to exterior surface 22 . Piezo-electric element 90 is electrically connected to an energy storage device 92 which may take the form of a coiled spring and/or a flywheel 94 . Energy storage device 92 is electrically connected to an electrical load 96 that may take the form of a sensor 98 .
[0018] During flight, changes in altitude of and/or turbulence on, an aircraft 2 may result in dimensional changes to exterior surface 22 and/or interior surface 24 or other parts of body 4 . The dimensional changes are realized by piezo-electric element 90 . In response to the dimensional changes, piezo-electric element 90 generates a flow of electrical energy that is passed to energy storage device 92 and used to power electrical load 96 . In this manner, power may be provided for an electrical load without the need for long runs of conductors that increase complexity, manufacturing costs, and an overall weight of the aircraft. The number of energy harvesting devices may vary and can be located on any surface of body 4 .
[0019] At this point it should be understood that the exemplary embodiments describe a system for harvesting electrical energy from an aircraft resulting from changes in altitude and/or turbulence. Harvested electrical energy is passed to a local energy storage device and used to power electrical loads. In this manner, long runs of electrical cables that carry electrical energy from a central electrical source to loads may be reduced. The reduction in cabling leads to increased operational capacity and efficiencies of the aircraft. It should also be understood that the number and type of energy harvesting members may vary. Also, an aircraft may include various types of energy harvesting members. In addition, the number and type of electrical storage devices and electrical loads may vary, and some loads or storage devices may be located in low pressure zone 28 attached to exterior surface 22 .
[0020] While the invention has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the claims.
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An energy harvesting system for an aircraft includes an energy storage device, and an energy harvesting member electrically connected to the energy storage device and mechanically linked to the aircraft. The energy harvesting member is configured and disposed to generate an electrical energy output in response to one of a change in altitude of, or turbulence on, the aircraft.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to an apparatus for removing acid constituents such as HCl and so-called SO x from the waste-gas generated in a combustion apparatus such as a combustion furnace, an incinerator and the like which burns materials containing elements of Cl and/or S, by the use of calcium-containing chemisorbent. It is intended by the term "chemisorb" to mean chemically absorb or adsorb, or absorb or adsorb with simultaneous chemical reaction.
2. Discussion of Background and Material Information
It has been known that the waste-gas generated by refuse incinerators includes a small amount of HCl gas originating from Cl-containing organic polymers such as polyvinyl chloride and polyvinylidene chloride. Again, waste-gas resulting from combustion of sulfur-containing materials is invariably contaminated by SO x or gaseous oxidized products of sulfur, with, in general, about 99 percent thereof being SO 2 and the rest, SO 3 .
There are two types of gas purification processes of the wet-process and the dry-process. The former emcompasses scrubbing the gas with an aqueous solution or suspension of such a chemisorbent as NaOH, Na 2 SO 3 , CH 3 COONa, NH 3 , Ca(OH) 2 , Mg(OH) 2 , MgSO 3 , or basic aluminum sulfate. Whereas the wet-process has the merits or advantages of intensive removability, easy workability and scarceness of environmental pollution, in general the equipment required for this purpose is rather complex and expensive and requires a considerable amount of space for its construction. On the other hand, the dry-process is advantageous in that it is in smaller in size, less expensive to construct, and is simpler in operation.
The chemisorbants used in the dry-process are mostly calcium compounds mainly for economical reasons, although aluminum coated with sodium oxide, hydrated manganese oxide and copper oxide were once claimed to be effective. Of the calcium compounds, calcium hydroxide, calcium oxide and calcium carbonate are by far the most suitable in view of availability, effectiveness and economy. Among them, calcium carbonate is somewhat different from the others in that it is a salt and less reactive. However, the occurrence of the following chemical reactions at higher temperatures of about 800° to 1000° C. makes choice among them less important.
CaCO.sub.3 --CaO+CO.sub.2 ( 1)
Ca(OH).sub.2 --CaO+H.sub.2 O (2)
Care should be taken in the case of CaCO 3 , therefore, to maintain these temperatures for sufficient time to enable the reaction (1) to proceed.
In a typical conventional dry-process using calcium hydroxide as the chemisorbent, particulate calcium hydroxide suspended in air is blown into the duct of waste-gas maintained at higher temperatures, to form a lean fluidized flow within the duct which moves downstream. During its migration a substantial amount of chemisorption of the acid gases occurs, and eventually reaches an electrostatic precipitator wherein the solid powder is electrostatically removed. In the case where calcium carbonate is used as the chemisorbent, it is preferable to charge the powder into higher temperature zones of above 800° C. to increase the rate of the aforementioned reaction (1).
The amount of the calcium compounds used was at most two times the stoichiometric or chemical equivalent because excess amounts incur squandering of electrical energy and are not economical. The extent of dechlorination is commonly 40 to 60%, the same being the case for desulfurization.
It will be desirable that the extent of removal of the acid constituents is increased without increased load for the electrostatic precipitator.
SUMMARY OF THE INVENTION
It is, accordingly, an object of this invention to provide an apparatus for removing the acid constituents more satisfactorily from the waste-gas by the use of particulate calcium compounds without increased load for the electrostatic precipitator.
Another object of this invention is to provide an apparatus for removing the acid constituents from the waste-gas which does not use aqueous solution or dispersion.
To accomplish these and other objects, this invention contemplates an apparatus wherein powder consisting of one or more species of the calcium compounds is blown into a duct for the waste-gas to form a lean fluidized flow moving downstream until it reaches a vertical moving bed filter located cross wise with respect to the direction of the waste-gas. During this period of time the chemisorption proceeds to a substantial extent. The powder suspending gas is filtered with simultaneous chemisorption by the moving bed filter having louvered walls for the gas passage and a layer of granular particles which, in turn, capture the calcium by carrying out the chemisorption in steps, i.e., in the duct and in the filter bed, permits the reaction to proceed closer to completion so that a greater stoichiometric amount of calcium compound then heretofore thought possible can be introduced into the moving bed filter without an increased load on the electrostatic precipitator. Inasmuch as the vertical moving bed filter can be of almost any width, an uneven gas flow therethrough is essentially avoided.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is an elevational schematic illustration of the separation apparatus with the near side walls taken off to show the inside construction.
FIG. 2 is a generalized flow diagram showing how the apparatus of this invention is integrated into a full purification system.
FIG. 3 is a graphical representation showing the relationships between the extent of removal of HCl as the acid constituent and the stoichiometric ratio (chemical equivalent) of Ca(OH) 2 to HCl.
FIG. 4 is a graphical representation denoting the relationships between the extent of removal of SO x as the acid constituent and the stoichiometric ratio (chemical equivalent) of Ca(OH) 2 to SO x .
FIG. 5 is a graph showing the general trend of the extents of powder removal and of HCl gas removal with an increased moving velocity of the packed moving bed for the case of FIG. 3.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring first to FIG. 2, which exemplifies a general arrangement of equipments, the waste-gas generated in a refuse incinerator 1 flows to the right through a duct 2, and into this duct the particulate calcium compound or compounds processed elsewhere to an air suspension is added at an appropriate location designated as 8. The resultant air suspension flows downstream in a fluidized state and reaches a moving bed filter 3. The chemisorption reaction takes place in large part in duct 2, and further proceeds in moving bed filter 3, in the presence of the calciumaceous powder captured and retained therein. The waste-gas substantially freed from large-size particles and the acid gas leaving the filter 3, further moves to an electrostatic precipitator 4 wherein small-size particles passed through filter 3 uncaptured are electrostatically removed. The waste-gas is then drawn by the exhaust 5 to stack 6 and released therefrom to the air.
Referring back to FIG. 1, there is schematically depicted the integral part of this invention in more detailed way. The waste-gas at a temperature of, about 600° C. for Ca(OH) 2 and above 800° C. for CaCO 3 in the case of SO x removal, whereas about 300° to 400° C. in the case of HCl removal, enters the duct 2 from left to right along the arrow. The duct 2 is provided with a plurality of holes 8a perforated through the wall thereof which open into an annular roofed area having a C-shaped cross section which opens inwardly. The two open side edges of the roofed area are secured air-tightly to the outer surface of the duct to form an annular pathway 8b for the air suspension. The annular pathway is, in turn, connected to a dust former 9 through pipe 8c. The dust former 9 consists essentially of a blower 9a and a dusting box 9b, the boosted air from the former being used to make up air suspension of the particulate calcium compound under severely turbulent condition. The pulverizer of the calcium compound is not shown because it relates little to this invention, except the charge chute 9c is shown in the figure.
The flow of the waste-gas in duct 2 is made sufficiently turbulent to maintain a fluidized state and to prevent sedimentation of the powder. A substantial part of the chemisorption occurs within duct 2, because a greater amount of the calcium-aceous powder can be used due to the use of the moving filter bed without causing more load to the electrostatic precipitator. The waste-gas suspending the powder then reaches the vertical moving bed filter 3 wherein the powder is filtered off from the gas by the materials used for packing the bed which includes captured powder in addition to conventional natural and artificial packing materials as discussed below. The second step or finishing chemisorption reaction, further occurs in the bed, and, in fact, in more vigorous way, since the acid components in the waste-gas have more chances to make contact with the captured powder.
The moving bed filter 3 consists essentially of a moving bed 3a, louvered front and rear walls 3b1, 3b2, adjustable speed charging valve 3c and discharging valve 3d (in the figure, both of so-called star gate valve type), and a hopper 3e. The louvers of the walls 3b1 and 3b2 have rising slopes from inside of the bed to outside to prevent spilling out of the particulate mass constituting the bed. It is to be noted that the distance between walls 3b1 and 3b2 referred to as depth of the bed is deeper at the upper part of the bed wherein less calciumaceous powder is retained because exposure of the bed to the powder-suspending gas is shorter than in the lower part, narrow of the bed wherein the exposure is made for longer time, and the powder content is more.
Many known materials of natural and artificial origin can be used satisfactorily as the packings for the moving bed. Among them, however, gravel is one of the most appropriate in view of the cost and its irregular shape and widely distributed size for retaining the powder. The moving bed constituting mass moving down by gravity and leaving from the discharging valve 3d is introduced into a mechanical screen 7 and separated to the oversize consisting practically of packings and the undersize consisting mainly of the partly reacted powder. For simplicity, driving means for the sieve 7a is not shown. The receiving funnel 7b collects the undersize and drops it out through chute 7c. On the other hand, the oversize leaves the sieve at the lowermost part thereof designated as 7d. Overhung weir 7e is provided to level off the mass on the sieve. The moving or falling speed of the moving bed should be fast enough for the calciumaceous powder not to spill out from the louvered walls and also not to exhibit excessive pressure loss, and slow enough for the moving bed to contain a sufficient amount of the powder, to prevent the powder from passing uncaptured through the intergranular space. It is of course advantageous that enough powder is added, in advance, to the packings in hopper 3e to prevent short-passing of the powder-suspending waste-gas at the upper part of the filter bed 3a.
In FIGS. 3 and 4, there are shown the relations between the extents of removal of the acid constituent and the stoichiometric ratio of Ca(OH) 2 to the acid constituent, the differences being that HCl is used in the former case and SO x , in the latter case, and the temperatures are 350° C. and 700° C. for respective cases. The curved line I represents the result in the case of no moving bed filter, the curved line II, the result in the presence of the moving bed filter, and the curved line III, half of the undersize is added to the fresh powder at the dusting box 9b, from the charge chute 9c so that the suspending powder is increased by that amount of about 1.5 folds. In FIG. 3, when the value of the abscissa is 4, the ordinates of the curved lines I, II, and III are 70%, 87%, and 93%, respectively. Whereas when the abscissa designates 7, the curved lines I, II, and III give the ordinates of 88%, 97 %, and 98%, respectively. In a similar way, in FIG. 4, when the value of the abscissa is 4, the ordinates of the curved lines I, II, and III are 45%, 75% and 90%, respectively, and when the abscissa is increased to 7, the ordinates of the curved lines I, II, and III are, respectively, 68%, 92%, and 98%. The results indicate the effect of providing the moving bed filter and increasing, at the same time, the stoichiometric ratio of the calcium compound straight-forwardly.
The packings used in the moving bed such as gravel have, in usual, properties sufficiently tolerable against abrasion and cracking, so that they can be used repeatedly by such a way as of recharging the oversize resulting from the screen 7 into the hopper 3e. As shown in FIG. 2, the apparatus includes means for recycling oversized particles to the moving bed through conduit 12 which conveys the oversized particles to the source of packing material. The apparatus also includes means for recycling at least part of the undersized particles through conduit 13 which communicates between the means for classifying and the source of packing material. In addition, the apparatus may also include means for recycling at least part of the undersized particles through conduit 14 to the duct in communication between the means for classifying and the means for forming a suspension.
As is clear from the above description, the moving bed filter 3 has dual functions of filtration or powder removal and, of chemisorption. However, as can be seen in FIG. 5, the extent of powder removal reduces with an increased moving velocity of the moving bed, on the contrary, the extent of HCl removal increases with the increased moving velocity. Therefore, care should be taken to choose an approprite moving velecity.
The waste-gas leaving the moving bed filter which is substantially freed from the acid constituents and the particulate mass, then proceeds to the electrostatic precipitator 4 wherein, as well known, smaller-size particles of less than about 20,000 nm in diameter are effectively removed. The apparatus shown in FIG. 1 is intended to represent a conventional Hot Cottrel type having parallel plates 4a as collecting electrodes and a number of rods 4b placed midway between the collecting electrode plates as discharging electrodes. The conveyor 12 just below the electrostatic precipitator 4 is used to carry out the collected dust through the discharging valve 14 from the chamber 10 which encloses both the moving bed 3a and the electrostatic precipitator 4 with casing 10a, to reduce the dust trouble in the working environment.
The apparatus shown in FIG. 1 and described above is of horizontal type in which the powder-suspending waste-gas flows horizontally and the vertical moving bed filter mentioned above is built crosswisely to the flow. The alternative vertical version in which the powder-suspending waste-gas flows vertically to a horizontal moving bed filter, is practicable with appropriate design change. In fact, the horizontal moving bed filter through which a gas passes vertically, is more common in the chemical industry, and may afford better performance in the respect that the gravitational force acts just perpendicular to the bed, and at least in principle, the calciumaceous powder is captured and retained evenly throughout the horizontal bed area, provided that the bed depth is equal everywhere and the packings of the bed are feeded therefor and drawn therefrom uniformly. It is, of course, very difficult to satisfy these provisions. The vertical version described above is preferred in that the bed depth is substantially invariable with time as a result of the presence of the two sustaining louvered walls.
While this invention has been particularly shown and described with reference to a preferred embodiment thereof, it is to be understood by those skilled in the art that the foregoing and other changes on form and details can be made without departing from the spirit and scope of this invention.
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An apparatus for removing acid constituents such as HCl and/or SO x from the waste-gas generated by furnaces,incinerators and the like wherein the calcium-containing powder material is blown into a waste-gas duct to form a lean fluidized flow until it reaches a vertical moving bed filter having two louvered walls between which granular packings are filled. The process for removing the acid constituents is accomplished by chemisorption which occurs first in the duct and then in the filter bed. A recycled use of the powder is preferred. The filtered waste-gas is further purified by an electrostatic precipitator. The use of a moving bed filter permits the use of a greater amount of calciumaceous powder relative to the acid gases without increasing the electrical load on the electrostatic precipitator.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not applicable.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to improvements in the construction and manufacture of polymeric bags. In particular, the present invention relates to improvements in the construction and manufacture of polymeric bags for use in trash compactors.
[0004] 2. Description of the Related Art
[0005] Polymeric bags are ubiquitous in modern society. The widespread adoption and use has resulted in polymeric bags being available in different combinations of material, capacity, thickness, dimensions and color. In terms of potential applications, polymeric bags may be used for product packaging, long-term storage of goods, food storage, and trash collection among other uses. In response to consumer demand, manufacturers of polymeric bags have developed innovative, new technology over the years to improve the utility and performance of polymeric bags. The present invention described herein is one such improvement and is of particular interest to the use of polymeric bags for residential or office trash compactors.
[0006] Trash compactors are used in numerous applications to reduce the volume of a particular amount of waste material that must be hauled away and disposed. In commercial settings, trash compactors are frequently used to compact cardboard boxes and other bulky paper material into smaller sizes. In this example, the compacted cardboard can then be bundled and shipped off for recycling or reprocessing. Reducing the volume of the cardboard material results in less frequent trips to haul the material away for recycling, meaning increased efficiency as a result of reduced transportation costs. It is also common to find compactor bags in home and office settings in the form of under-the-counter trash compactors. Like their commercial counterparts, the home and office compactors minimize the size of the trash that must be hauled away. The present invention is directed primarily toward bags used in such under-the-counter trash compactors.
[0007] Trash compactor bags are a good example of a niche market of trash bags. Trash compactor bags must be specially designed to address the unique challenges presented by use in a residential or office trash compactor. Several different types of bags have traditionally been used in connection with trash compactors. One example of a trash compactor bag is the heavy paper compactor bags which are similar to paper grocery store bags. The paper compactor bags are usually sized to fit in standard-sized compactors, but must be specially coated with a plastic film or other liquid-impermeable layer to prevent leakage of the paper bag when liquids are present. The coating layer and the higher costs of paper bag manufacture make paper compactor bags markedly more expensive than plastic compactor bags, which in contrast do not require special coatings.
[0008] Although plastic compactor bags do not require special coatings to prevent leakage of liquids placed in the compactor, plastic compactor bags must be significantly stronger than similarly sized plastic trash bags for several reasons. First, the compactor mechanism itself raises a risk that the bag will be punctured or torn during operation—either by the compactor mechanism itself or by objects in the trash compactor being forced into the sides of the bag. Additionally, as plastic compactor bags carry significantly more trash by weight than an typical trash bag of the same physical size, the plastic compactor bag must be stronger than a typical plastic trash bag to ensure that it does not rip when the bag is being carried or during removal from the compactor. Therefore, a thicker, stronger bag is used to reduce the risk of puncture or tear.
[0009] One of the biggest problems with plastic bags used in home or office trash compactors is that the bags are not rigid and therefore cannot stand on their own within the receptacle of the trash compactor. Therefore, the upper opening of the plastic compactor bag must be secured over the upper lips of the trash receptacle. Furthermore, as the trash compactor mechanism operates to compact the trash, it has a tendency to pull the sides of the plastic bag downward and can even result in the bag falling into the receptacle. To attempt to address these issues, plastic compactor bags in the prior art have been designed to be significantly longer than the height of the trash compactor receptacle. The longer length is used to pull the upper opening of the bag far down over the upper lips of the receptacle. However, after compaction, a person may still need to readjust the bag by pulling the bag over and around the receptacle.
[0010] Drawstrings have not historically been incorporated into trash compactor bags for several reasons. First, the manufacturing processes of thicker drawstring bags are significantly more complicated than those used to manufacture thinner drawstring bags. All drawstring bags require that certain holes and cut-outs be provided in the drawstring bag while also requiring that the drawstrings be sealed within hems located at the top of the bag. These processes are significantly more difficult as the thicknesses of both the bag material and the drawtape increase. Additionally, prior art drawstring bags adapted for use with a trash compactor would suffer from the same deficiencies as twist-tie or wave-cut bags. In particular, typical prior art drawstring bags would still require considerable additional length to allow the bag to be sufficiently pulled over the upper lips of the receptacle. The additional length required increases the amount of material needed to manufacture the bag, which in turn drives up the cost of the product.
[0011] To address the foregoing challenges, the present invention introduces a new apparatus and method for keeping compactor bags securely on the trash receptacle by providing an elastic drawstring trash compactor bag. The present invention addresses the need for a trash compactor bag which provides a positive gripping force around the outside of a trash receptacle when placed thereon. The present invention further addresses the need for a bag which does not require any additional length or the use of superfluous material to allow the bag to be sufficiently pulled over and around the receptacle of a trash compactor.
SUMMARY OF THE INVENTION
[0012] The present invention is directed toward an improved construction of trash bag for use in a trash compactor. In particular, the present invention is directed toward an elastic drawstring trash compactor bag, the bag having an upper opening, at least one hem located along the upper opening of the bag, and at least one elastic drawstring disposed within the at least one hem. The upper opening of the bag defines a circumference of the bag being less than 50 inches in a relaxed state. When a force is exerted by a person in an outward direction along the upper opening of the bag, the circumference of the bag can be expanded to be greater than 50 inches in a stretched state. Furthermore, the upper opening of the bag retracts and grips the receptacle when the outward force is removed.
[0013] It is contemplated that the present invention may be utilized in ways that are not fully described or set forth herein. The present invention is intended to encompass these additional uses to the extent such uses are not contradicted by the appended claims. Therefore, the present invention should be given the broadest reasonable interpretation in view of the present disclosure, the accompanying figures, and the appended claims.
BRIEF DESCRIPTION OF THE RELATED DRAWINGS
[0014] A full and complete understanding of the present invention may be obtained by reference to the detailed description of the present invention and preferred embodiment when viewed with reference to the accompanying drawings. The drawings can be briefly described as follows.
[0015] FIG. 1 provides an elevation view of an elastic drawstring trash bag as contemplated by one embodiment of the present invention.
[0016] FIG. 2 provides a perspective view of an elastic drawstring trash bag as contemplated by one embodiment of the present invention.
[0017] FIG. 3 provides a cross-sectional view of the hem region of an elastic drawstring trash bag as contemplated by one embodiment of the present invention.
[0018] FIG. 4 provides an enlarged view of the short seal region of an elastic drawstring trash bag as contemplated by one embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The present disclosure illustrates one or more preferred embodiments of the present invention. It is not intended to provide an illustration or encompass all embodiments contemplated by the present invention. In view of the disclosure of the present invention contained herein, a person having ordinary skill in the art will recognize that innumerable modifications and insubstantial changes may be incorporated or otherwise included within the present invention without diverging from the spirit of the invention. Therefore, it is understood that the present invention is not limited to those embodiments disclosed herein. The appended claims are intended to more fully and accurately encompass the invention to the fullest extent possible, but it is fully appreciated that certain limitations on the use of particular terms is not intended to conclusively limit the scope of protection.
[0020] An elevation view of an elastic drawstring trash compactor bag 100 is depicted in FIG. 1 to illustrate a preferred embodiment of the present invention. The same embodiment is also depicted in a perspective view in FIG. 2 to provide a better understanding of the present invention. In the depicted preferred embodiment, the elastic drawstring trash compactor bag 100 is a polyethylene bag constructed from a first panel 102 and a second panel 104 . The elastic drawstring trash compactor bag 100 has two side edges 108 and a bottom 106 . The upper edges 112 of the first panel 102 and second panel 104 define the upper opening 120 of the elastic drawstring trash compactor bag 100 . The length of the bag from the upper edges 112 of the bag to the bottom 106 of the bag is preferably 25 to 35 inches in length.
[0021] In the depicted embodiment, the first and second panels 102 and 104 are formed from a single polyethylene sheet which is folded in half. The fold of the polyethylene sheet forms the bottom 106 of the elastic drawstring trash compactor bag 100 . After the polyethylene sheet is folded, side seals 110 are provided which run substantially the entire length of the bag along a line spaced slightly inside the sides 108 of the first and second panels 102 and 104 . Although this is the preferred method of construction, a person of ordinary skill in the art would recognize that the present invention is not necessarily limited to this construction method and that alternative bag construction techniques may be used without diverging from the spirit of the present invention.
[0022] As can be better seen with reference to FIG. 3 , an elastic drawstring 116 is disposed within hems formed in the elastic drawstring trash compactor bag 100 . To provide the hems for containing the elastic drawstrings 116 , the uppermost portion of the first and second panels 102 and 104 are folded over the elastic drawstrings 116 . A hem seal 114 is then provided on each panel 102 and 104 to close the hem, encapsulating the elastic drawstrings 116 within the respective hem. The hem seal 114 may generally be formed by applying a combination of heat and pressure to each panel, sealing the two layers of polyethylene film together. Furthermore, the bag 100 may provided with air ventilation holes 122 which allow the air within the hem to escape during manufacture and use.
[0023] The materials used in constructing the present invention are markedly thicker than those used in a typical plastic trash bag. For example, the typical thickness of the first and second panel in a traditional drawstring trash bag as known in the prior art may only be in the range of 0.6 to 1.2 mils (0.0006 inches to 0.0012 inches). However, the thickness of the first and second panels 102 and 104 for an elastic drawstring compactor bag as disclosed herein would typically be between 1.75 to 3.25 mils, and preferably in the range of 2.0 to 2.5 mils. Likewise, the elastic drawstrings 116 are also thicker than drawstrings used in an typical trash bag known in the prior art.
[0024] The drawstrings in a typical trash bag are generally 1.5 to 2.5 mils in thickness. Drawstrings are commonly made predominantly from high density polyethylene which results in the drawstrings resisting a tendency to stretch. Furthermore, in the event that the typical drawstring stretches after applying a large amount of force, it will not retract in any meaningful way. In construction of the depicted embodiment of the present invention, a combination of elastomers and polyethylene materials are used to provide an elastic drawstring 116 that stretches a certain amount when an outward force is applied to the elastic drawstring 116 . More importantly, the elastic drawstring 116 retracts when the force is removed. The elastic drawstring 116 of the present invention is generally between 3 mils and 6 mils in thickness, with a preferred thickness of approximately 4.5 mils.
[0025] FIG. 4 is an enlarged view of the upper corner of an embodiment of the present invention. In FIG. 4 , the short seal 118 can be seen that is located in the upper corner of the elastic drawstring trash compactor bag 100 . The short seals 118 are provided to seal the first panel 102 and the second panel 104 to the respective ends of the elastic drawstrings 116 disposed within each hem. Furthermore, each short seal 118 welds a large area of the first panel 102 to the second panel 104 .
[0026] Looking now back at FIG. 2 and FIG. 3 , the width of the upper opening 120 of the elastic drawstring trash compactor bag 100 is defined by the distance between the inner edges of the two short seals 118 . The total circumference of the upper opening is therefore two times the distance between the inner edges of the two short seals 118 . The standard home or office trash compactor has a rectangular trash receptacle with dimensions of approximately nine inches by sixteen inches. Therefore, the total circumference of the trash receptacle of the trash compactor is approximately fifty inches. A large majority of trash compactors have a trash receptacle with a circumference within one linear inch of this size. Therefore, the upper opening 120 of the elastic drawstring trash compactor bag 100 may be selected to provide a circumference, in a relaxed state, of less than 50 inches, preferably 46-49 inches.
[0027] When a force is applied, the elastic drawstrings 116 are elongated. As a result, the elastic drawstrings 116 will stretch with the first panel 102 and the second panel 104 , and consequently the circumference of the upper opening 120 will increase to allow the upper opening 120 of the bag to stretch over the upper lips of a compactor trash receptacle. After stretching the upper opening 120 over the upper lip of the trash compactor receptacle, the force is removed and the elastic drawstrings 116 will have a tendency to retract. Since the circumference of the trash receptacle is greater than the upper opening 120 of the bag, the elastic drawstrings 116 will contract to fit around the trash receptacle, providing a holding force for the bag. The holding force reduces the likelihood that the elastic drawstring bag 100 will fall into the receptacle during use of the trash compactor.
[0028] As noted, the embodiments depicted herein are not intended to limit the scope of the present invention. Indeed, it is contemplated that any number of different embodiments may be utilized without diverging from the spirit of the invention. Therefore, the appended claims are intended to more fully encompass the scope of the present invention.
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The present invention is directed toward an elastic drawstring trash compactor bag, the bag having an upper opening, a hem located along the upper opening of the bag, an elastic drawstring disposed within the hem, the upper opening of the bag defining a circumference of less than 50 inches in a relaxed state, and the upper opening of the bag being expandable such that the exertion of force expands the circumference in a stretched state. Furthermore, the upper opening of the bag retracts when the exertion of force is removed.
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FIELD OF THE INVENTION
[0001] The present invention generally relates to interne browsing portable devices. More specifically, the invention addresses a watch that receives updated content from a pre-selected group of web pages and keeps it cached in the watch memory for ready access by the user.
BACKGROUND OF THE INVENTION
[0002] The underlying concept is that people are interested in having updated information on certain specific topics continually available, but don't want to go through the hassle of connecting to a network, looking for the specific source, etc. Once the interest in checking certain information arises, people want to have it immediately. As people habitually check their wrist watches on a regular basis, it is desirable to have said updated information made readily available in this device with no need to ask for it. However, the typical size and weight restrictions associated with the small footprint of a wrist watch require ingenuous power management. Ideally, the Network Module of the wrist watch does not remain powered up while not needed, as the watch does not have the power to supply the circuitry required to remain continually connected to the network.
[0003] The connection to the web using a portable device typically involves a certain delay associated with connecting to a remote server over a wireless network. When the user wishes to have access to the most up-to-date information on the weather, stock market, news, etc. the process of accessing said information involves the steps of powering up the portable device, logging onto the network, accessing a remote server, navigating to the website that contains the desired information and waiting until said information is displayed on the device.
[0004] The prior art includes US 2002/0,059,166 by Wang, which discloses a method for parsing web codes which involves the selection of web content and its storage in portable devices. The selected content is not updated automatically, requiring active intervention by the user to connect to the web and request an update of the content previously stored in the portable device. Furthermore, Wang does not address the power management issues associated with a small footprint portable device.
SUMMARY OF THE INVENTION
[0005] According to a certain aspect of the present invention, the portable device is a watch that offers immediate access to regularly updated content of a previously selected group of web pages without requiring it to keep continually connected to the network. The concept takes advantage of the portability and convenience of a wrist watch and aggregates to it a customizable web browsing capability. A carefully designed power management scheme harmonizes the need of frequent data update with the small footprint of the watch, which imposes restrictions in the size and therefore storage capacity of the battery. The update schedule is user-customizable and once connected to the network, the watch behaves exactly like a typical portable web-browsing device.
[0006] The above as well as additional features and advantages of the present invention will become apparent in the following written detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] A more complete understanding of the present invention may be had by reference to the following detailed description when taken in conjunction with the accompanying drawings, wherein:
[0008] FIG. 1 is a perspective view illustrating a wrist watch according to an aspect of the present invention;
[0009] FIG. 2 is a schematic drawing illustrating the basic elements of the communication network and the flow of data between them according to an aspect of the present invention;
[0010] FIG. 3 is a schematic drawing illustrating the selection of the report list web pages with the wrist watch connected to a domestic computer logged to a specific web page according to an aspect of the present invention.
[0011] FIG. 4 is a plan view illustrating the front panel of a wrist watch according to an aspect of the present invention;
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0012] The wrist watch is small and compact, which imposes restrictions on the size—and therefore storage capacity—of the battery that can be used to power it and thus require judicious allocation of the available power. In order to reconcile the amount of energy that would be required for keeping the Network Module circuitry energized at full power with the small footprint of the device—which externally looks like an ordinary wrist watch—the invention utilizes specific power management schemes both in the watch CPU Module and the Network Module circuitry. The use of remote processing, where the application the user is operating is actually run by a remote server instead of running in the watch itself, allows for further power saving.
[0013] Physical Description of the Watch
[0014] According to an exemplary embodiment of the present invention, the wrist watch frequently receives the updated contents of selected web pages from a remote web server over a wireless network. The remote web server gets updated contents from these selected web pages on a continuous basis. The watch is continually connectable to a cellular phone network, such as a GSM, GPRS, CDMA or 3G, which is the data part of the network. The watch features an image display of 70 pixels by 140 pixels, dedicated directional arrow keys in the front panel for scrolling up, down, left and right. A virtual keyboard can be brought up on the touch-sensitive screen of the image display. The user can touch the image display and drag the content around like in the Apple® i-Phone®.
[0015] Regarding function, the watch can be divided in three main structures: a display, a CPU Module and a Network Module. The visual interface with the user utilizes a display incorporating bi-stable technology that can retain an image without power. Once the Image is formed in the display, it does not require any power to remain there, which contributes to minimizing power consumption. The crystals that make up the display surface may exist in one of two stable orientations (typically black and “white”, although it can also be colored), and power is only required to change the image displayed. The watch incorporates a wireless communication system that includes a dedicated module for web connection, henceforth referred to as the Network Module. The Network Module incorporates an RF antenna and a modem unit. The connection between the watch and the Internet is established via wireless link to cell phone towers or equivalent wireless infrastructure. The connection between the watch display and the watch Network Module is made through the watch CPU Module. The watch internal CPU Module incorporates cache memory for storing web page content, as well as a real time clock.
[0016] Independently of the various power management schemes that will be detailed further below, the watch CPU Module runs a routine for ensuring that the time displayed in the watch panel is always correct. The aforementioned routine has the CPU Module switching itself ON at regular time intervals—for instance every half an hour—and energizing the watch panel bi-stable display. It then compares the time indicated the watch display to that indicated in the real time internal clock. If they are different the watch corrects the time displayed, basing said corrections on the real time clock integrated in the watch CPU Module.
[0017] A certain menu of customized web pages can be selected by the user at home, by logging on to a specific web page from his/her home computer. These are henceforth referred to as the report list web pages. There is a number of standard web pages—for example 3—that is pre-selected by the service provider company. Although the user cannot remove the standard web pages from the report list, there is an option for changing or formatting certain details on them. Further aspects of the watch operation are user-customizable through the service's web page. The user can customize the content on each of the pre-selected web pages. For example, it is possible to have the e-mail application page regularly storing in the watch cache memory enough data to allow the user to see more than one page of text, typically made accessible through the use of the directional arrow keys in the watch panel.
[0018] Once logged on the specific web page of the service provider server and into his/her particular User Profile, the user has access to tools that allow actual design of the pages that will be displayed in his watch. Among the features that can be included in each specific web page of the report list, the user can custom-select specific threshold events that will trigger the sending of a Threshold Update Message from the server. For instance, said threshold events can be the arrival of an e-mail at the remote server, the report of a goal scored on a hockey game or the report of a certain stock rate hitting a pre-selected level. The user can drag and drop elements of the page from a menu, see a preview of the display, set up the threshold events that will trigger transmission of an immediate update from the server to the watch, etc.
[0019] Once the user is done designing his selected WebPages and these are stored in his user profile, the server sends the designed display image—respecting the selections of elements, size, etc. as selected by the user—to the watch for the user to see it. The format of the report list web pages is stored in the CPU Module cache memory as an image. The content of each report list webpage is conveyed to the user by means of the page's image, and said image content is updated periodically when new images are received from the remote server, in a process denominated Remote processing that will be detailed further below.
[0020] Once the user selects those web pages that will be included in the report list, the user-selected pages and the service provider's standard choice pages are uploaded to that user's watch. The report list is uploaded to that specific user's profile in the service provider's server, so that the server keeps track of which pages shall be regularly updated for that specific user's watch. In a typical scenario, the user would have six web pages in the uploaded report list: weather, news and face book—pre-selected by the service provider company—plus e-mail inbox, sport scores and specified stock tickers, custom-chosen by that particular user. As discussed in detail further below, the remote server frequently sends to the watch an update for the content of these six selected web pages. Each of these constantly updated pages contains a representation of the corresponding home page, including any links displayed in it. The content of these report list web pages is stored in the cache memory of the watch CPU, which makes it immediately available at any time for the user with no need for actual connection to the web. If however the user chooses to view data that is beyond what is stored in these report list web pages—for instance navigating to a web page that is not in the report list—the desired content is acquired from the web in real time, with the Network Module connecting to the web and affording regular navigation from the watch.
[0021] The service provider's server performs a graphic size conversion in order to adapt the web page size and layout to the dimensions of the watch display. This size conversion however is performed only for the pre-selected web pages on the report list. For other pages accessed during navigation the user must scroll through the page in order to see the whole of it, as the size of the watch display is smaller than that of a standard computer screen.
[0022] Introduction of the Power Management Scheme
[0023] The specific power management schemes implemented in the watch CPU Module and the Network Module circuitry will now be described.
[0024] For the CPU Module circuitry there are two stages of powering: OFF, in which the CPU Module is not powered, and ON in which the CPU Module is running at full power. For the Network Module circuitry there are three different powering states: In the OFF powering state the circuitry is not powered. In the Standby Mode powering state the Network Module behaves much like a standard cell phone: Most of the time it remains unpowered; interspersed with short periods in which the Network Module escalates to the minimum power status required for sending brief, periodical pulses to the nearest network tower, with the Network Module circuitry returning to the unpowered status right after broadcasting these brief pulses in case there is no pending connection request. In a typical scenario, these pulses last for 1 millisecond and are sent on every 2 seconds, prompting for any connection request by the remote web server. When a prompt meets a server connection request, the Standby Mode is escalated to full power, in the manner to be described in detail further down. The third powering state is ON, wherein the Network Module circuitry is in continual full power.
[0025] The powering states of both the CPU Module and Network Module of the watch change according to the passing of time and/or user action, and will be best understood in the following description of the operation of the watch itself.
[0026] Description of the User Just Checking the Cached Content without Switching the Network Module ON
[0027] For most of the time both the CPU Module and the Network Module are in their OFF powering state and the watch display exhibits the main page, as illustrated in FIG. 1 . That includes the display of the time plus a condensed data set on each of the report list web pages. An example of condensed data set for the weather would comprise a numeric indication of the current temperature, a pictorial indication of the weather and an indication of the data source. These condensed data sets perform as icons, and when the user clicks on them the watch displays the corresponding web page with the full data set as stored in the CPU Module cache memory. The user defines how many of the report list web pages will have their condensed data set displayed on the main page, and the display size of each condensed data set is automatically optimized for the available display space.
[0028] In a first embodiment of the invention, the user can scroll through the individual pages corresponding to the condensed data sets depicted on the main page by pressing the arrow keys in the panel of the watch or pressing one of the condensed data sets displayed on the touch-sensitive screen. The pressing of any of the arrow keys or condensed data sets triggers the switching ON of the watch CPU. As the CPU Module in switched ON, the data stored in the cache memory is made available and the user can scroll through each individual web page with the full data set as stored in the CPU Module cache memory, which is depicted in the watch display. Provided that the user does not click on any links that might be featured on a report list web page, the Network Module is not switched ON. Once a certain period of time elapses with no further action by the user, the CPU Module switches itself back to the OFF state.
[0029] In an alternative embodiment, once the CPU Module is switched ON by the pressing of any of the arrow keys or condensed data sets in the watch panel, the CPU Module switches ON the Network Module in anticipation of the user intention of navigating, which is materialized once the user actually clicks on any of the links provided in the report list web pages. Once a certain period of time elapses with no further action by the user, the CPU Module switches the Network Module and then itself back to the OFF state.
[0030] Description of how the Elapsing of a Preset Time Triggers the Switching ON of the Network Module and Also Triggers the Download of Web Content Update
[0031] In a second embodiment of the invention, a period of time is previously set for the cyclic switching ON of the watch CPU. Once said preset time value elapses—for instance every 10 minutes—the watch CPU Module goes from the OFF state to the ON state. Then the CPU Module switches the Network Module power state from OFF to the Standby Mode, and the Network Module prompts the network for any connection request by the remote web server.
[0032] In case the server indeed has a pending connection request, the CPU Module immediately escalates the powering state of the Network Module from the Standby Mode to ON, after which the connection between the Network Module and the remote server is sought. Once the Network Module is ON, the establishment of the connection to the network takes from 8 to 10 seconds, during which an hour-glass animation on the watch display reports to the user that such connection is being established. Once the connection is established, the Network Module updates the 6 report list web pages by downloading any changes to their display images from the remote server to the watch cache memory. As soon as the watch CPU Module establishes that the download is complete, connection to the web is interrupted and the Network Module circuitry is powered OFF. The Network Module remains powered OFF until the next cycle of periodical prompting, which in the given example would happen 10 minutes later.
[0033] In case the server has no pending connection request, the CPU Module switches the Network Module circuitry OFF. The Network Module remains powered OFF until the next cycle of periodical prompting, which in the given example would happen 10 minutes later. As previously described, if the user does not click on any of the links featured on the report list web pages and a certain period of time elapses with no further action by the user, the CPU Module switches itself back to the OFF state and the watch display exhibits the main page, with the condensed data sets already incorporating any changes as recently stored in the cache memory. This arrangement allows for very small net energy consumption, and is the power management scheme of choice in the primary embodiment envisaged for the present invention. All the while the watch display exhibits the main page, with any changes as recently stored in the cache memory.
[0034] Description of the Network Module Working in Standby Mode as Default
[0035] In a third embodiment of the invention, the watch CPU Module is kept powered ON and the Network Module is continually kept on the Standby Mode. In a manner similar to the standard operation of a cell phone, it sends brief, periodical pulses to the nearest network tower. For instance these pulses last for 1 millisecond and are sent on every 2 seconds, prompting for any connection request by the remote web server.
[0036] In case the server has no pending connection request, no immediate action is taken and the Network Module remains in the Standby Mode.
[0037] In case the server has a pending connection request, the Network Module—that was so far in the Standby Mode—escalates its powering state to ON, and then seeks connection with the remote server over the Internet. Once the Network Module is ON, the establishment of the connection to the network takes from 8 to 10 seconds, during which an hour-glass animation on the watch display reports to the user that such connection is being established. Once the connection is established, the Network Module updates the 6 report list web pages by downloading any changes to their display images from the remote server to the watch cache memory. As soon as the watch CPU Module establishes that the download is complete, connection to the web is interrupted and the Network Module circuitry returns to the Standby Mode, remaining in it until a further periodical pulse meets a new connection prompt. All the while the watch display exhibits the main page, with any changes as recently stored in the cache memory.
[0038] The net energy consumption of this embodiment is higher compared to the one of the primary embodiment. However, it has the advantage of higher frequency of cache memory update, avoiding the delay imposed by the power management scheme that prompts for updates only after the cyclic interval, for instance every 10 minutes.
[0039] Description of a Preset Event Triggering the Switching of the Network Module ON
[0040] In a fourth embodiment of the invention, the watch CPU Module is kept powered ON and the Network Module is continually kept on the Standby Mode, in a manner similar to the standard operation of a cell phone.
[0041] Following the custom settings previously recorded on each of the report list web pages on the user profile at the remote server, the server sends to the watch a Threshold Update Message whenever one of the specified threshold events occur, such as the arrival of an e-mail at the remote server, the report of a goal scored on a hockey game or the report of a certain stock rate hitting a pre-selected level. This message is received on the very next opportunity, namely the next time the watch Network Module prompts for any connection request by the remote web server according to the Standby Mode cyclic schedule—for instance two seconds later. As the prompt meets the server connection request, the Standby Mode is escalated to full power, the connection between the Network Module and the server is established and the Threshold Update Message will push to the watch cache memory a non-cyclic update. This sequence of events will be triggered by the happening of any one of the customizable threshold events specified by the user. Again, all the while the watch display exhibits the main page, with any changes as recently stored in the cache memory.
[0042] The scope of custom options made available to the user upon specifying threshold events includes the setting of custom audio alarms to be broadcast by the watch for each particular threshold event, so that the user can enjoy a convenient and timely notification upon the occurrence of threshold events.
[0043] In an alternative embodiment, the user is allowed to set up the elapsing of a time interval as the threshold event, according to the hired service plan and the model of the watch.
[0044] Description of the User Clicking of a Link in One of the Report List Web Pages, Starting Up Regular Navigation and the Use of Remote Processing
[0045] In a fifth embodiment of the invention, while the CPU Module and the Network Module of the watch are switched OFF, the user uses the arrow keys to scroll through the report list web pages or presses one of the condensed data sets displayed on the touch-sensitive screen and thus triggers the switching ON of the watch CPU. When the user clicks on any of the links featured on the report list web pages, the CPU Module switches the Network Module ON.
[0046] In an alternative embodiment, once the CPU Module is switched ON by the pressing of any of the arrow keys or condensed data sets in the watch panel, the CPU Module switches ON the Network Module in anticipation of the user intention of navigating, which is materialized once the user actually clicks on any of the links provided in the report list web pages.
[0047] Once the Network Module is ON, the establishment of the connection to the network takes from 8 to 10 seconds, during which an hour-glass animation on the watch display reports to the user that connection is being established. After that—once the network connection is established between the Network Module and the remote server—navigation is as fast as the bandwidth allows, and the watch initiates regular web navigation using remote processing, as described below.
[0048] Description of the Remote Processing
[0049] The situation in which the user is reviewing content that is stored in the watch CPU Module cache memory has already been described. When the user chooses to view data that is beyond what is stored in the report list web pages, the watch performs the role of a portable browsing device, and the remote processing mentioned earlier in this description comes into play. The remote processing is employed whenever the user is browsing any web pages that are not cached in the CPU Module memory, being thus core to the invention and available in all of its embodiments.
[0050] Although there is no delay to suggest it to the user, the watch CPU Module does not run the application itself. The application operated by the user—be it a browsing application, an e-mail application or some other application—is actually run at the remote server, and the watch plays the role of a visual interface between the user and the virtual display of the remote server where the application is being run. In other words, the watch displays for the user the image he/she would be seeing in the screen of the remote server if it were in visual range.
[0051] The transmission from the remote server to the watch is streamlined to contain no more than bitmap images plus any navigational links that may be featured on the webpage. For example, when the server gets an update on weather forecast, the corresponding data is depicted in the server's virtual display. In order to make this updated information available for the watch user, the server rasterizes said updated image from its virtual display, compresses it and transmits it to the watch in blocks or frames over the Internet; the watch stores said updated image in cache memory and makes it readily available for the user to see in the watch display. For those web pages included in the report list, the server converts the updated image following the custom sized design set on the User Profile before rasterizing, compressing it and transmitting to the watch; for the web pages that are not in the report list the images are sent in their standard size and the user has the option of scrolling vertically and horizontally to display the whole image in the watch screen, which is smaller than the standard computer screen for which the pages were originally designed.
[0052] The images that appear on the watch display are bitmap images. Besides regular text and pictures, said images may include graphic representations of web navigation links, software command buttons and other elements through which the user communicates his intentions to the remote running application. The user clicks on an element on the watch display based on his visual identification of its image. The watch transmits the graphic coordinates of this click to the remote server. Once the click coordinates are received by the server, where the actual application is running, the server processes the corresponding click. If the click causes the application to perform some action—such as navigating to a different web page or performing a given software command—the application takes the requested action, updating the image on the server's virtual display accordingly. The remote server then rasterizes and compresses the updated bitmap image and transmits it in blocks or frames to the watch. This data is received by the watch, rendered by the watch CPU Module and presented in the watch display for the user. As the actual processing is performed in the remote server, the workload of the watch CPU Module is low and the user is kept abreast of the processing by the continued updating of the image presented in the watch display.
[0053] While this invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from its spirit and scope.
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The invention discloses a wrist watch that offers immediate access to regularly updated content of a previously selected group of web pages without requiring it to keep continually connected to the network. The concept takes advantage of the portability and convenience of a wrist watch and aggregates to it a customizable web browsing capability. A carefully designed power management scheme harmonizes the need of frequent data update with the small footprint of the watch. The update schedule is user-customizable and once connected to the network, the watch behaves exactly like a typical portable web-browsing device.
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This invention relates to a process for reducing the health hazard caused by the use of asbestos as a building material. In particular, the invention relates to a process which substantially prevents the escape of minute fibres of asbestos from the base material into the atmosphere.
Asbestos fibre has been used as a building material for acoustic and heat insulation for many years. The use of asbestos includes thermal insulation for the fire-proofing of steel, as acoustic sound absorbent material on walls and ceilings, as lagging on hot water and steam pipes and of course as asbestos-cement building sheet having many applications. Recently however the material has become recognised as a possible major health hazard through the inhalation by occupants of the buildings of dust and fibres released from the asbestos cladding.
Whilst buildings are no longer insulated with the material, the very large number of existing structures having asbestos present in some form poses a major problem.
It is appreciated that there is only a minimal health hazard from the installation and use of asbestos-cement sheet however asbestos dust fall-out is prolific from the other sources mentioned above. Some health authorities claim this fall-out is highly dangerous due to its carcinogenic effect on living tissue. Cases are known where asbestos dust from thermal insulation fitted to top-floor plant rooms of large buildings has been continually forced through the entire building via air conditioning ducts. In such cases, management is faced with the heavy cost of the closure of the building for removal and replacement of the asbestos material with a safer substitute. Not only is the replacement of the material expensive but many local government authorities will not allow the waste asbestos materials so produced to be dumped at normal waste disposal areas.
BRIEF DESCRIPTION OF THE INVENTION
My invention renders buildings having asbestos installations safe for occupation by treatment in situ. It has been found that the process can be applied with minimal inconvenience to normal use patterns since treatment can be made out of normal working hours if desired. Further, there is no problem disposing of what little waste material remains from the application process, since this contains little or no asbestos.
In accordance with the present invention therefore there is provided a process for treatment of asbestos or other fibrous materials comprising a first step of substantially saturating, with the application of pressure, the asbestos material with a binder being a polymeric resin, and a second step of applying a polymeric resin compound comprising polymeric resin and a filler.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates the steps of rolling the fibrous asbestos to distribute the resinous material throughout.
FIG. 2 illustrates rolling the fibrous material using a polyethylene sheet 22 to cut down drag on the roller.
FIG. 3 illustrates removal of the polyethylene film after rolling is complete.
FIGS. 4 and 5 illustrate the thin metal probe used in the non-destructive testing of the degree of saturation of the asbestos base.
DETAILED DESCRIPTION OF THE INVENTION
One preferred form of this invention consists of a process enabling substantially complete impregnation of the porous asbestos or other fibrous insulation material 14 by a non-flammable binder, said binder consisting of a polymeric resin such as vinyl acetate homopolymer or a copolymer with not less than 70% by weight vinyl acetate, said polymeric resin being plasticised with either a non-flammable organic plasticiser (such as tri-dichloropropyl phosphate, chlorinated paraffin or tri-tolyl phosphate) or a humectant type plasticiser (such as a solution of sodium metasilicate containing a small quantity of polyhydric alcohol or a glycol). The preferred embodiment also provides for application of a roller 16 to assist impregnation of the binder into the material. The polymeric resin may be either a water emulsion or a solution in an appropriate solvent.
The binder solution/emulsion should have an active non-volatile binder content of between 10%-50% by weight. Further, the solution/emulsion at the working concentration as applied by the process described below should have a surface tension less than 50 dynes/cm. This will minimise the tendency of a wet roller acting on a loose fibrous surface to drag off fibers and particles by the surface tension of the liquid film between the roller surface and the wetted material.
Reduction of this drag is further achieved by a foaming action to the formulation. This leads to foam generation by the squeezing action of the roller on a porous resilient layer containing both air and the applied liquid. Such foam has less drag than a liquid film, against the separation of the roller. To maximise saturation of the layer of insulation, the viscosity of the applied binder should be as low as possible, and in any case less than 100 cps. Further, the binder is required to have a pronounced surfactant wetting action on fine fiber and dust having the surface characteristics of asbestos and fiberglass.
When dry, the film of cured binder must have the following indices of flammability as per test method of AS1530 prt 3 1976:
______________________________________ (a) For deep impregnation (b) For final coat only, with of exposed surface, finishing or for deep impr. outer coating in flammableIndex (AS1530 pt. 3) of (b) situations______________________________________Ignitability (0-20) less than 14 less than 1.0Spread of flame (0-10) 0 0Heat evolved (0-10) less than 3.5 0Smoke developed (0-10) less than 5.5 0______________________________________
In use, my invention provides for a solution having the above properties to be applied to the asbestos substrate by a low-pressure airless spray operating in the range 15-500 psig (approximately 100 to 3500 kiloPascals). The lower pressure limit is that necessary to ensure adequate atomisation of the liquid spray as fairly large droplets for maximum penetration of the insulation, and the upper limit is determined by the necessity to avoid unnecessary disturbance of the fibrous matt and creation of consequent dust hazards in the operation. This spraying is continued to the degree of maximum feasible saturation as indicated by visual checking, with the limit indicated by runoff of excess liquid.
Then, whilst the treated layer is still wet, and before any significant loss by evaporation occurs, this embodiment of our invention provides for insulation 14 on substrate 10 to be briefly compressed by a roller 16 as shown in FIG. 1. This roller preferably incorporates a non-stick coating 18 on a firm base 20, such as a polytetrafluoroethylene coating (Teflon) over a cylinder of hard rubber or metal.
The squeezing of a resilient porous material with enough free liquid present causes movement of the liquid to penetrate entirely through the material thus compressed, wetting the entire mass of the spongey material through to the substrate interface. The roller causes up to 75% compression.
It has been found that the applied roller pressures necessary to achieve this on average asbestos or fiberglass insulation may lie between 10 and 150 kiloPascals, depending on the thickness thereof, the proportion of cementitious material originally present in the insulation when applied, and on other factors.
In certain conditions of very loosely-applied insulation, especially where there is only a small quantity of the original cementitious binder present, the surface of the insulation may be so deteriorated as to be extremely difficult to treat with the stated liquid impregnations and compress sufficiently for complete saturation. The action of squeezing/rolling may cause pulloff of the surface fibers, or even large sections of the insulation, despite the surface tension and foaming properties of the formulations described above.
As illustrated in FIGS. 2 and 3, a technique for overcoming this tendency has been developed by first saturating by spraying as above, then temporarily stretching a sheet of clear plastic 22 (polythene or similar) across the area to be compressed. The roller compression is then applied over the plastic screen, which effectively prevents drag between the roller and the treated insulation material. When the insulation has been fully impregnated, the plastic sheeting is removed by a peeling action, drawing it away from the surface at an acute angle (less than 30°, as per attached sketch). The use of a transparent sheeting enables visual observation of progress of the roller squeezing action. Final checking of the degree of saturation is of course done with the electrical device outlined below.
To achieve adequate stability of the applied treatment it is necessary that all the fibrous insulation material be uniformly treated with the stabiliser liquid, from the outer surface through to its interface with the substrate. Hence a method of nondestructive testing of the degree of saturation is necessary in many cases, especially where the insulation exceeds approximately 100 mm thickness. A simple method of checking this forms a part of this invention. The device employed is illustrated in FIGS. 4 and 5 and consists of a thin metal probe 24 having an insulated sleeve, which is inserted through the asbestos/fiberglass so that the tip 26 of the probe contacts the surface 12 of the substrate 10 only. A potential of between 1 and 15 volts D.C. is applied between the probe and a spring-loaded backplate electrode 28 in contact with the outer surface of the treated insulation.
The resultant current flow is of a magnitude determined by the degree of saturation of the insulation, and of its thickness. The current may be measured directly on a micro-ammeter 34, or by a transistorised device containing a trigger circuit tuned to the characteristics of the binder being applied and the insulation being treated.
In the device here preferred, an audible tone indicates whether there is a sufficiency or deficiency of the treatment liquid present. If insufficient, the spray application and rolling is repeated until there is an adequate degree of impregnation indicated in the area tested.
In general, dry insulation has an electrical conductivity nearly zero at the applied voltage. When sufficiently impregnated with the binder stated at the formulations above, the conductivity whilst still wet will be in excess of 100 microSiemens. The test device is therefore normally set for a change of audio signal at this level, although it is normally necessary to set the device for the parameters of the particular situation in each case.
The following are typical formulations suitable for the first step of our asbestos stabilising process as described above.
(A) Formula using vinyl acetate homopolymer or vinyl acetate/acrylic copolymer emulsions (by weight):
______________________________________ Usu- ally Limits______________________________________1. Water 35%2. Dissolve ammonium bromide powder 10% (3% to 20%)3. Premix nonionic surfactant @ 1% (0.1% to 5%) and tri-dichloropropyl phosphate* 4% (5% to then stir into main batch 25% of #4)4. Stir in unplasticised vinyl acetate** 50% (15% to homopolymer emulsion, approx 40-50% 75%) resin content5. Top up with water to total batch 100%______________________________________ @ such as TERIC GN9 ex ICI. *such as FYROL FR2 ex Stauffer Chemical Co. **such as VINAMUL 63076 ex A.C. Hatrick Chemical OR MACROMOL VS2 ex Field Group Polymerics. The chemical formula of the main ingredients are as follows: Polyvinyl acetate = generally (CH.sub.2 :CH:C.sub.2 H.sub.3 O.sub.2).sub.x (polymerises on drying) plasticised with Tridichloropropy phosphate = (ClCH.sub. 3 O).sub.3 PO or Tritalyl phosphate (CH.sub.3 C.sub.6 H.sub.4 O).sub.3 PO
(B) Formula using sodium metasilicate (by volume):
______________________________________1. Water 24-12. Sodium metasilicate solution 150-1 (40% to 80% of 40% solids (typically type N40 total) ex ICI)3. stir in glycerol OR sorbitol 5-1 (1% to 10% OR ethylene glycol of #2)4. stir in nonionic surfactant 1% (0.1% to 5% of typically ICI Teric GN-9 total batch)5. top up with water to batch total 200 liters______________________________________ The chemical formula of the main ingredients are as follows: Sodium metasilicate (generally) (Na.sub.2 O).sub.x (SiO.sub.2).sub.y.nH.sub.2 O typically in this application (Na.sub.2 SiO.sub.3.5H.sub.2 O) (reversible plasticised with one of the following polyhydric alcohol (glycerol) CHOH(CH.sub.2 OH).sub.2 OR (sorbitol) C.sub.6 H.sub.8 (OH).sub.6 OR ethylene glycol CH.sub.2 OH.CH.sub.2 OH OR diethylene glycol CH.sub.2 OH.CH.sub.2.OCH.sub.2.CH.sub.2 OH
The tridichloropropyl phosphate of (A) above, and the polyhydric alcohols of (B) (for which certain ethylene glycols may be substituted) are included for the purpose of flexibility of the resulting cured adhesive bond. The unplasticised resin or raw sodium metasilicate is very brittle when dried, and such embrittlement would allow generation of dust if disturbed. The inclusion of such plasticisers gives a degree of flexibility to the film. However, plasticisers normally used for vinyl acetates and acrylics are unsuitable for this particular purpose, due to their inherent flammability. Since the insulation being treated is nearly always present as a fireproofing medium, the applied anti-dusting treatment must not degrade the flammability rating of the insulation.
Having ensured the resin has penetrated well into the asbestos mat, the polymer is then allowed to set to an elastic consistency, preserving must of the resilience and insulating properties of the untreated matrix, but increasing the tensile strength thereof sufficient to support the second polymer treatment described herein. The polymer requires properties appropriate for bonding together asbestos fibres and for bonding said fibres to the steel, concrete or other substrate.
It has been found that the usual asbestos insulation requires a total application of diluted resin formulations as described, to result in the deposition of between 30 and 180 grams of cured resin solids, per millimeter thickness, per square meter of insulated area, for optimum impregnation as imimised dust particle emission from the surface thus treated. The optimum quantity for a particular case depends on the porosity (i.e. degree of existing compaction) of the insulation, and on the quantity present of other filling or adhesive materials used in the original application of the asbestos insulation.
Having thus increased the tensile strength of the matrix the stabilized matrix may be overlaid with a sprayed application of a further polymeric material comprising a suitable polymer resin, silica sand, pigment and a fine ground mineral, said compound having a sprayable consistency. This compound is applied to a thickness of between 2 mm and 20 mm to form a hard protective coating to provide against physical damage or abrasion of the stabilized matrix of asbestos, which would possibly cause the undesirable release of further asbestos fibre. In most applications the primary resin used in the second stage is in fact the same resin used in stage one, however other compatible resins may be used, provided they pass flammability tests AS1530 pt. 3.
The pigment is used principally for decorative purposes although it has some heat reflective function also. A fine ground mineral such as chalk, calcite or other bio-compatible mineral acts as a filler for the resin.
It is essential that the protective coating take to the asbestos matrix and thus stage two can be applied either when stage one is tacky or, provided the stage two resin is sufficiently adhesive, after the asbestos matrix has become hard. It is also important that the protective coating have a slight elastomeric property to prevent fractures. The decorative film so applied is water porous, which prevents scaling off of the film which has been a disadvantage of previous methods of application due to build up of vapour pressure within the substrate. Whilst the pores are sufficiently large to be porous to water vapour, they are on the other hand too small to allow the passage of asbestos dust.
Both resin solutions must be free of all forms of asbestos filler, vinyl chloride monomers, styrene monomers, toxic pigments and other substances known to present a health hazard.
Application of the armouring compound is carried out on quite a different principle, being designed both for minimum impact damage to the asbestos matrix and for a minimum amount of deflection, and thus wastage, of sprayed resin particles.
A further advantage over the prior art is found in this invention. In existing methods of treating asbestos insulation with materials to prevent dust and fallout, the surface is commonly sprayed with liquids such as paints, or other film-forming substances, to saturation point of the surface.
It has been found that this process frequently leads to collapse of the insulation, especially from the underside of ceilings thus treated, caused by the weight of the applied fluid in mechanically-weak layers of insulation. The additional weight causes layers of saturated insulation to fall away, during the inevitably extended period between application and hardening of the paint, resin, etc. Such paints or other liquids thus contained in a thick layer of porous material (asbestos) are effectively shielded from normal drying process of air, heat, and light, and may take many days to fully harden.
This problem is overcome by a two-stage application of the two adhesive systems described in this patent application. Asbestos insulation is first saturated with the plasticised sodium metasilicate and whilst still fully wet is additionally overtreated with the polymeric adhesive. Roller compression of the treated insulation then causes blending of the two liquids now present within the insulation.
It has been found that such blending or other contact between the two liquids results in immediate gelling of the combined system. This gelling results in immediate stiffening and increased cohesion of the treated insulation, thus substantially lessening the tendency to physical collapse under the weight of applied liquid.
It has also been found that the resin treatments described also provide a degree of protection in buildings against the occurrence of vermin in the fibrous insulation thus treated. In some situations, untreated fibrous insulation becomes infested with fleas, cockroaches or other vermin. The presence of the resin impregnation makes such infestations less likely, due to the ammoniacal and alkaline salts in the cured system.
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Process for the impregnation of asbestos or other fibrous material, comprising, as a first step, impregnating, with the application of pressure, the material with a polymeric resin binder to substantially saturate the material with binder and, as a second step, applying a polymeric resin compound comprising a polymeric resin and a filler. The process of the invention substantially prevents the escape of minute fibers of asbestos into the atmosphere, and so reduces the health hazard associated with asbestos.
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TECHNICAL FIELD
[0001] The disclosed inventive concept relates to vehicle air conditioning systems and particularly to the evaporator of such systems. More particularly, the disclosed inventive concept relates to a baffle for an evaporator tank wherein the baffle is a cladded and folded plate having elevated areas, the baffle being brazed or otherwise attached to the evaporator tank.
BACKGROUND OF THE INVENTION
[0002] Most vehicles today include air conditioning systems to provide for improved occupant comfort. While being first introduced in the automotive world several decades ago, air conditioning systems have changed little. Thus the fundamental parts of the modern vehicle's air conditioning system are known and understood. These parts include the compressor, the condenser, the evaporator, the thermal expansion valve, and the drier or accumulator. In many ways the compressor is the heart of the vehicle's air conditioning system. The compressor pressurizes hot gaseous refrigerant and forces it on to the condenser. The condenser, which is like a small radiator, cools the hot gases received from the compressor. As these gases cool, they become liquid in the condenser.
[0003] Liquid refrigerant leaves the condenser under high pressure and enters the drier or accumulator. The drier catches any liquid water that may inadvertently have entered the system. The liquid refrigerant, once cleared of any water, flows to the expansion valve which functions to remove pressure from the liquid refrigerant and literally allows it to expand. This reduction of pressure allows the liquid refrigerant to return to the vapor stage in the evaporator, the refrigerant's next stop.
[0004] The evaporator is also similar in shape and function to a small radiator. Typically the evaporator is fitted inside of the vehicle's passenger compartment in or around the instrument panel. The still-liquid refrigerant enters the evaporator under low pressure from the expansion valve. The liquid refrigerant vaporizes while absorbing heat from inside the car. Cold air is circulated within the passenger compartment by a fan that pushes air across the fins of the evaporator. Low pressure refrigerant, now in gaseous form, exits the evaporator and returns to the compressor where the cycle is repeated.
[0005] Evaporators are typically manufactured from aluminum and usually include an upper tank, a lower tank and a series of refrigerant-containing tubes fitted there between. Baffles are located within the tanks to regulate the flow of liquid refrigerant. The baffles are usually brazed to the inner wall of the tank. However, known technology makes positioning the baffles during the brazing process challenging and frequently results in the baffles being out of alignment prior to the brazing process.
[0006] Accordingly, an improvement in evaporator design and assembly is required to overcome the challenges faced by the prior art.
SUMMARY OF THE INVENTION
[0007] The disclosed inventive concept overcomes the problems associated with known evaporators by providing an arrangement in which the baffles are fixed in position prior to brazing to provide an accurate and fluid-tight seal without error and with minimum production time. The disclosed inventive concept provides an evaporator that includes an evaporator core, an evaporator tank attached to the evaporator core, and at least one single-piece and folded baffle having raised surfaces incorporated into the evaporator tank.
[0008] The evaporator tank includes an interior wall. The raised surface has a wall-contacting portion that is in contact with the interior wall. More particularly, the baffle has two opposed sides. Each of the opposed side has a raised surface defined by a pair of opposed raised surfaces. The baffle further includes a top edge and a side edge. The pair of opposed raised surfaces is provided adjacent one of the edges and includes two pairs of opposed raised surfaces. One of the two pairs of opposed surfaces is provided adjacent the top edge of the baffle and the other of the two pairs of opposed surfaces is provided adjacent the side edge of the baffle. The raised surface is selected from the group consisting of a flat-sided ramp, a curve-sided ramp, and a dimple.
[0009] The above advantages and other advantages and features will be readily apparent from the following detailed description of the preferred embodiments when taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] For a more complete understanding of this invention, reference should now be made to the embodiments illustrated in greater detail in the accompanying drawings and described below by way of examples of the invention wherein:
[0011] FIG. 1 is an isometric view of a evaporator according to the disclosed inventive concept;
[0012] FIG. 2 is an exploded view of the upper portion of the evaporator of FIG. 1 showing the upper tank in spaced apart relation to the cooling fins and the end plate assemblies and baffles also spaced apart from the upper tank portions;
[0013] FIG. 3 is a perspective view of a baffle according to the disclosed inventive concept illustrating the baffle being folded from a single sheet of material;
[0014] FIG. 4 is a perspective view of a baffle according to a first embodiment of the disclosed inventive concept;
[0015] FIG. 5 is an end view of the baffle of FIG. 4 ;
[0016] FIG. 6 is a perspective view of a baffle according to a second embodiment of the disclosed inventive concept;
[0017] FIG. 7 is an end view of the baffle of FIG. 6 ;
[0018] FIG. 8 is a perspective view of a baffle according to a third embodiment of the disclosed inventive concept;
[0019] FIG. 9 is an end view of the baffle of FIG. 8 ;
[0020] FIG. 10 is a perspective view of a portion of upper tank portions shown in cutaway and illustrating baffles according to the disclosed inventive concept;
[0021] FIG. 11 is a view taken along line 11 of FIG. 10 ;
[0022] FIG. 12 is a top plan view of a portion of upper tank portions shown in cutaway and illustrating baffles according to the disclosed inventive concept;
[0023] FIG. 13 is a view taken along line 13 of FIG. 12 ; and
[0024] FIG. 14 is an end view of a single-layer baffle according to an alternative embodiment of the disclosed inventive concept.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0025] In the following figures, the same reference numerals will be used to refer to the same components. In the following description, various operating parameters and components are described for different constructed embodiments. These specific parameters and components are included as examples and are not meant to be limiting.
[0026] The evaporator for use with an air conditioning system for a vehicle according to the disclosed inventive concept is illustrated in its various embodiments in FIGS. 1 through 13 . However, it is to be understood that the illustrated embodiments are suggestive and are not intended as being limiting.
[0027] The evaporator of the disclosed inventive concept is illustrated in FIG. 1 while the baffles and end plates are illustrated in FIG. 2 . The evaporator of the disclosed inventive concept is a multi-pass evaporator having a thickness range of between about 25 mm and 80 mm. Various embodiments of the baffles are shown in FIGS. 3 through 9 . FIGS. 10 through 13 illustrate the baffles in place in the tank portions. Regardless of the embodiment, the evaporator of the disclosed inventive concept overcomes challenges and limitations associated with the construction of current evaporators.
[0028] Referring to FIG. 1 , an evaporator, generally illustrated as 10 , is shown. The overall configuration of the evaporator 10 as illustrated is intended as being suggestive and not limiting.
[0029] The evaporator 10 includes an upper tank assembly 12 and a lower tank assembly 14 . The upper tank assembly 12 and the lower tank assembly 14 are typically made of a metal, although other materials including polymerized materials may be used alone or in combination. A lower pressure, liquid refrigerant input 16 is provided as is a lower pressure, gas refrigerant output 18 . The liquid refrigerant input 16 is connected to liquid input upper tank portion 20 . The gas refrigerant output 18 is connected to a gas output upper tank portion 24 . A series of refrigerant-containing tubes 26 fluidly connect the upper tank assembly 12 and the lower tank assembly 14 .
[0030] Referring to FIG. 2 , an exploded view of the upper portion of the evaporator 10 is illustrated in spaced apart relation to the refrigerant-containing tubes 26 , a pair of baffles 27 , and a pair of end plate assemblies 28 . One of the end plate assemblies 28 is shown separated into its two portions, an inner end plate 30 having an inlet refrigerant input passageway 31 and an outlet refrigerant output passageway 32 , and an outer end plate 33 having an inlet refrigerant input port 34 (connected to the liquid refrigerant input 16 ) and an outlet refrigerant output port 36 (connected to the gas refrigerant output 18 ). The illustrated shapes of the baffles 27 , the inner end plate 30 and the outer end plate 33 may be altered from the illustrated shapes without varying the scope of the present invention.
[0031] FIGS. 3 through 9 illustrate various embodiments of the baffle of the disclosed inventive concept. A single type of baffle may be used in a single tank or different embodiments of the baffle may be used.
[0032] In FIG. 3 , a perspective view of the baffle 27 is illustrated. The baffle 27 is preferably stamped from a single piece of cladded sheet aluminum and is then folded as illustrated to form the two-layer baffle of the disclosed inventive concept. The baffle 27 includes a first baffle half-portion 38 and a second baffle half-portion 40 .
[0033] The folding of the baffle 27 provides spring back that helps to retain the baffle 27 inside the evaporator tank. This feature results in a robust brazing process to prevent any internal refrigerant leaks.
[0034] In addition to folding as a method of retaining the baffle 27 in its pre-brazed position within the tank, the baffle 27 is also provided with raised areas that contact the inner wall of the tank. In this way, the baffle 27 is held in place during the brazing process. In addition to FIG. 3 , this arrangement according to a first embodiment of the disclosed inventive concept is also illustrated in FIGS. 4 and 5 .
[0035] A pair of opposed upper ramped raised areas 42 and 42 ′ are provided to contact the inside top wall of the tank while a pair of opposed lower ramped raised areas 44 and 44 ′ are provided to contact the inside side wall of the tank. In combination with the springing action of the folded baffle 27 , the ramped raised areas 42 , 42 ′, 44 and 44 ′ retain the baffle 27 in its proper aligned position to allow correct brazing of the baffle 27 in place within the tank.
[0036] FIGS. 6 and 7 illustrate raised areas according to an alternate embodiment of the disclosed inventive concept. Particularly, a baffle 50 is showing having a first baffle half-portion 52 and a second baffle half-portion 54 . A pair of opposed, upper semi-circular raised areas 56 and 56 ′ and a pair of opposed, lower semi-circular raised areas 58 and 58 ′ are formed on the baffle 50 . In combination with the springing action of the folded baffle 50 , the semi-circular raised areas 56 , 56 ′, 58 and 58 ′ retain the baffle 50 in its proper aligned position to allow correct brazing of the baffle 50 in place within the tank.
[0037] FIGS. 8 and 9 illustrate raised areas according to a third embodiment of the disclosed inventive concept. Particularly, a baffle 60 is showing having a first baffle half-portion 62 and a second baffle half-portion 64 . A pair of opposed, upper dimpled raised areas 66 and 66 ′ and a pair of opposed, lower dimpled raised areas 68 and 68 ′are formed on the baffle 60 . In combination with the springing action of the folded baffle 60 , the dimpled raised areas 66 , 66 ′, 68 and 68 ′ retain the baffle 60 in its proper aligned position to allow correct brazing of the baffle 60 in place within the tank.
[0038] Beyond the configurations of the raised areas illustrated in FIGS. 3 through 9 , other configurations are possible, provided contact is made between the raised area and the upper or side wall of the interior of the tank. Accordingly, the embodiments shown are intended as being suggestive and not limiting.
[0039] FIGS. 10 through 13 illustrate adjacent baffles 27 in position relative to the upper tank in various views. Particularly, is a perspective view of a portion of an evaporator 10 shown in cutaway and illustrating side-by-side baffles 27 while FIG. 11 is a view taken along line 11 of FIG. 10 . The ramped raised areas 42 and 42 ′ are illustrated as being in contact with an inner wall 70 of the gas output upper tank portion 24 . The other raised areas (not shown) are also in similar contact.
[0040] FIG. 12 is a top plan view of a portion of an evaporator 10 shown in cutaway and illustrating more particularly the side-by-side relationship of the baffles 27 according to the disclosed inventive concept. FIG. 13 is a more detailed view of the side-by-side arrangement of the baffles 27 taken along line 13 of FIG. 12 . Once the baffles 27 are positioned inside of the tank portions 20 and 24 , the baffles 27 are brazed in position, thus permanently securing the baffles 27 inside the tank portions 20 and 24 .
[0041] FIG. 14 illustrates an alternative approach to a baffle according to the disclosed inventive concept. As shown in this figure, a flat plate baffle 42 is formed from a non-folded, single layer of material. The flat plate baffle 42 includes a first outer side 44 and a second outer side 46 . Formed on the first outer side 44 is a pair of raised areas 48 and 48 ′ and formed on the second outer side 46 is a pair of raised areas 50 and 50 ′. Because the flat plate baffle 42 is formed from a single layer, the positions of the raised areas 48 and 48 ′ are offset with respect to the positions of the raised areas 50 and 50 ′ due to manufacturing constraints. It is to be understood that while the raised areas 48 , 48 ′, 50 and 50 ′ are dimples, other configurations such as the ramps and semi-circles discussed above could be incorporated as well.
[0042] The disclosed inventive concept shown in the accompanying figures and described above effectively overcomes the problems known to be associated with known evaporators. By providing a system and method for properly aligning the baffles relative to the tank portions, proper brazing can be achieved.
[0043] While the preferred embodiments of the disclosed inventive concept have been discussed are shown in the accompanying drawings and are set forth in the associated description, one skilled in the art will readily recognize from such discussion, and from the accompanying drawings and claims that various changes, modifications and variations can be made therein without departing from the true spirit and fair scope of the invention as defined by the following claims.
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A evaporator provides an evaporator that includes an evaporator core, an evaporator tank attached to the evaporator core, and at least one single-piece and folded baffle having raised surfaces incorporated into the evaporator tank. The baffle has opposed sides having a pair of opposed raised surfaces. The baffle further includes a top edge and a side edge. The pair of opposed raised surfaces is provided adjacent one of the edges and includes two pairs of opposed raised surfaces. The raised surface can be a flat-sided ramp, a curve-sided ramp, or a dimple.
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TECHNICAL FIELD OF THE INVENTION
This invention relates to the separation of leukocytes and erythrocytes by sedimentation at normal gravity in the presence of a hydroxyalkyl cellulose. More particularly, this invention refers to a method for recovering approximately 80% of the original leukocytes whle leaving red blood cells intact. The leukocytes may be used in interferon production.
BACKGROUND OF THE INVENTION
Hydroxyethyl starch has routinely been used as a sedimenting agent [Lionetti, U.S. Pat. No. 4,004,975; Pestka, U.S. Pat. No. 4,289,690; Djerassi, U.S. Pat. No. 4,111,199; Chadha, U.S. Pat. No. 4,485,038; and Van Oss, et al., Immunol. Commun., 10(6), pp. 549-55 (1981)]. Treatment with hydroxyethyl starch ("HES") results in recovery of about 68% of the original pool of leukocytes or white blood cells ("WBC"). Ammonium chloride lysis yields 90% of the WBCs, but is undesirable in view of the wasteful destruction of the red blood cells ("RBCs").
Other agents which have been used as sedimenting agents are Dextran (glucose polymer), Ficoll (sucrose polymer), PVP, fenugreek seed extract, and phytohemagglutinins [Lichtenstein, U.S. Pat. No. 3,709,791; Chany, U.S. Pat. No. 3,560,611; Ferrante, U.S. Pat. No. 4,255,256; Guirgis, U.S. Pat. No. 4,152,208; Furuta, U.S. Pat. No. 4,409,106; Goore, U.S. Pat. No. 3,800,035; Shepherd, U.S. Pat. No. 3,594,276; Kirkham, U.S. Pat. No. 3,635,798; Widmark, U.S. Pat. No. 3,700,555].
Kanter, U.S. Pat. No. 4,487,700, refers to athixotropic barrier material of intermediate density to separate lymphocytes from erythrocytes and phagocytized leukocytes. Meyst, U.S. Pat. No. 4,283,289 refers to a leukocyte filter. The use of NH 4 Cl to lyse RBCs, while leaving most WBCs intact, is also known.
Hydroxyalkyl celluloses, and particularly hydroxyethyl cellulose, have been used as a thickening and stabilizing agent in pharmaceuticals and other compositions. However, they have never been used as sedimenting agents to separate lymphocytes from erythrocytes.
SUMMARY OF THE INVENTION
This invention relates to the use of hydroxyalkyl cellulose, particularly hydroxymethyl cellulose (HMC), hydroxyethyl cellulose (HEC) hydroxypropyl cellulose, (HPC), and hydroxybutyl methyl cellulose (HBMC) as sedimenting agents in blood cell separation. According to the present invention, about 80% intact leukocytes are recovered from the original number of leukocytes and over 95% of these remain in a viable state. Moreover, the erythrocytes which are separated into a lower phase, are also left intact.
The final concentration of HEC in the mixture is 0.05%, as compared to 3% HES in conventional separation methods. Accordingly, the harvested cells have relatively little HEC bound to them and may be washed off easily.
Unlike NH 4 Cl lysis, the HEC technique does not destroy granulocytes (granular leukocytes) or erythrocytes. Moreover, the WBCs recovered by this technique may be stored for at least one day without impairment of interferon production after exposure to an inducer.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a particularly efficient agent for sedimenting intact leukocytes without destroying red blood cells present in the blood sample. In order that this invention may be more fully understood, we have set forth the following examples. These examples are for illustrative purposes, and are not to be construed as limiting this invention in any way.
EXAMPLE I
We pooled, mixed and sampled buffy coats (American Red Cross) and determined initial RBC and WBC counts using the Cell Dyn 400 cell counter (Sequoia International). We prepared a sedimenting agent by making a solution of 0.1% of HEC (w/v) and 0.9% of NaCl (w/v) in deionized water, stirring for at least one half hour until the HEC goes into solution. The sedimenting agent was slowly mixed with the buffy coat pool for at least one minute, poured into a separatory funnel, or other suitable vessel and allowed to settle for one and one-half to three (1.5-3) hours at room temperature or cooler. The final concentration of HEC in the mixture is preferably 0.05% (w/v). However, HEC may be present in a final concentration of between 0.025% and 0.5%.
After separation was completed we either drained the bottom RBC layer or aspirated the top WBC layer. The bottom layer could then be resedimented with fresh sedimenting agent to capture more WBCs, as previously described.
We tested the collected layers for RBC count, WBC count, WBC/RBC, and WBC viability (by Trypan blue exclusion test). Our results are set forth below:
______________________________________ WBC/Sample Vol. RBC*10.sup.12 WBC*10.sup.10 RBC Yield______________________________________Experiment 1476-19(0.1% HEC, 0.9% NaCl stock solution)pool 600 ml 3.25 4.00 0.01 100%top layer 720 ml 0.20 3.37 0.17 84%bottom 500 ml 2.73 0.34 0.001 9%top layer 160 ml -- 3.12 -- 78%(afterwash)Experiment 1476-7(0.1% HEC, 0.9% NaCl stock solution)pool 1000 ml 5.88 4.66 0.01 100%top layer 830 ml 0.11 3.72 0.34 80%bottom 1190 ml 5.45 1.09 0.002 23%top layer 130 ml 0.07 3.58 0.51 77%(afterwash)______________________________________
We washed the harvested cells using centrifugation. The cells may alternatively be cleaned by using tangential flow filtration or other conventional methods.
The WBC layer was spun at 100×g for 7 minutes. We discarded the supernatant and resuspended the pellet in leukocyte medium at 37° C. and counted the WBC. We added the WBCs to a 2 liter volume of MEM medium, human serum, and alpha interferon primer at a concentration of 1×10 7 WBCs/ml. Induction took place in 6 liter round bottom flasks maintained in 37° C. water baths.
After an initial incubation period of 3 hours, we added Sendai virus to the flasks in order to induce alpha interferon production. The induction period was typically 18 hours. Alpha interferon was then collected by centrifugation at 4000 g's for 20 minutes. Samples of the supernatant were submitted for CPE (cytopathic effect) assay.
The CPE assay is based on the ability of alpha interferon to protect certain cells against certain viruses. In the assay used, Hep 2 cells were grown to confluence in 96 well microtiter plates. Serial dilutions of the alpha interferon were added to the sample wells and incubated with the cells (37° C., 5% CO 2 ) for about 20 hours. Next, VSV virus was added to the wells to infect unprotected cells. After an incubation period sufficient to achieve 100% cell death in the control wells (i.e., only cells and virus present in these wells), all wells were stained with Gentian stain. Intact cells appear purple due to the membrane picking up the stain. The well number (i.e., the dilution) at which 50% of the cells had been protected is called the endpoint. The endpoint was then used to correlate the titer of the sample (in units of interferon/ml.) to standards from the NIH.
When a stock solution of 0.05% HEC was used for cell separation, a very slow separation occurred. That is, when compared with separations using 0.1 and 0.2% HEC stock solutions, the 0.05% HEC separation had not proceeded as far as the latter two, in a comparable time period. Also, the 0.05% separation seemed to have more RBC contamination in the middle layer (as evidenced by a pink band rather than the white one seen in each of the other separations).
A stock solution of 0.5% HEC did not give a good separation--only two layers formed and more WBCs were recovered from the bottom layer than from the top layer. Also, the "purity" of the top layer, as expressed in terms of WBC/RBC, was less than 1/2 of that seen in the combined two upper layers of the 0.1% HEC separation (i.e., 0.14 compared to 0.30). Concentrations of 0.7 and 1.0% HEC were even less effective.
Over a series of experiments, we obtained alpha interferon titers in the range of 20-50,000 Units/ml.
We prepared a cytospin smear of HEC-collected WBCs. We treated the cells with MAY-GRUNWALD-GIEMSA stain, and inspected the cells microscopically. A cell differential study showed the leukocyte subpopulations to have essentially the same distribution as in the original blood pool. The morphology of the leukocytes was normal.
EXAMPLE II
We prepared a 0.1% solution of hydroxypropyl cellulose (300,000 m.w.; Aldrich Chemical) as described for HEC in Example I, above. The 0.1% HPC/0.9% NaCl solution was mixed with an equal volume of buffy coat pool. In two separate experiments, we observed good separation between WBCs and RBCs. However, because neither separation had been done in a separatory funnel, it was difficult to effectively collect the top layer without contaminating it with RBCs from the bottom layer.
We conducted the same type of experiments with hydroxybutyl methyl cellulose (HBMC). Using the same 0.1% concentration of polymer with 0.9% NaCl, the separation appeared to occur faster and looked better than a concurrently run HEC separation.
While we have hereinbefore presented a number of embodiments of this invention, it is apparent that our basic method can be altered to provide other embodiments which utilize the process of this invention. For example, the WBC yield may be increased by various means. First, sedimentation may be carried out in a device facilitating RBC/WBC separation. This would include a device having a constriction at the expected location of the RBC/WBC interface, or one having draining or aspirating means designed to minimize agitation of the interface. Second, a thixotropic agent may be added. Such an agent should be selected so that its specific gravity would cause it to collect into a barrier structure separating the RBC and WBC layers. Third, the extraction step could be repeated as desired with fresh sedimenting agent.
Other hydroxyalkyl cellulose could be substituted for HEC and HPC, as sedimenting agents.
In addition to unit gravity sedimentation, HEC might also be used in RBC/WBC separation by centrifugation. HEC may be used in the separation of cells from cell debris. Finally, the WBCs and RBCs provided by the present technique may be separated into WBC or RBC subtypes or fractionated to yield various WBC or RBC constituents.
The scope of this invention is to be defined by the claims appended hereto rather than by the specific embodiments which have been presented hereinbefore by way of example.
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Hydroxyalkyl celluloses are useful as sedimenting agents in the non-destructive separation of red and white blood cells. Intact WBC recovery is higher than with conventional methods. The white blood cells may be used in interferon production.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the field of video editing and especially to editing digitally stored video. It relates to a method of accomplishing editing using a QWERTY keyboard in a way that significant improves the speed of execution by an editor.
2. Background of the Invention
The process of editing video has been maturing since the 1960's. Systems that employ QWERTY keyboards for most editing functions have been common since the 1970's. Non-proprietary industry conventions have developed which allow editors to work on different systems without extensive retraining. Consequently, professional video editors have become extremely proficient at performing editing tasks by operating the keyboard while maintaining visual attention on the video source and edited material.
Modern video editing systems now employ digital storage of compressed video data. Such systems allow random access to a large number of video segments or "clips". Because video editors are now freed from the linear constraints of tape-based systems, digital storage based systems are commonly referred to as "non-linear". Common to most editing systems is a convention of video material coming from a "source" and going to a "recorder". While this approach originated in linear tape-based editing, it is still the norm for non-linear video editing systems.
Industry conventions have for many years placed source VCR selection on the "home row" of the QWERTY keyboard, i.e., the row comprising the characters "A", "S", "D", "F", "G", "H", "J", "K", "L" and ";". This convention has been used by editing systems from Ampex, ASC, Calaway, CMX, Grass Valley Group, Matrox, Sony, Strassner and others. The result of source VCR selection by a home-row key is simply an assignment of an editing system's machine control to a given VCR and an associated execution of a video switchpoint which displays video on a source or preview monitor. To perform the corresponding function in digital non-linear editing systems, editors have been required to take their eyes off their material, move a mouse to a thumbnail image representing a clip and execute source footage selection--usually by either double clicking on a mouse or dragging the material to the source side of an edit screen.
There is a perceived need in non-linear video editing systems to provide the editor with an improved method for accessing a desired video clip and thereby better utilize the capabilities of a digital storage-based system.
SUMMARY OF THE INVENTION
The present invention directly maps home row keys to video clips which have been logged, digitized, or imported into the editing system's database. This direct mapping of video clips to keys is distinctly different than the mapping of source VCR's to keys, in that all associated database records for a given clip, including provisional edit points, are instantly available. It also results in instant access to each clip without an editor having to take his/her eyes off the material being edited, which is a major advantage in editing where creative concentration is critical to story composition and productivity. This new process of the current invention is substantially faster for an editor than manual movement of a mouse, or other means provided by other systems, and represents a significant operational improvement in the state of the art of video editing.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified block diagram of a non-linear video editing system.
FIG. 2 is a partial view of a QWERTY keyboard used in a prior art video editing system.
FIG. 3 is a partial view of a QWERTY keyboard in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
In the following description, for purposes of explanation and not limitation, specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known methods, devices and circuits are omitted so as to not obscure the description of the present invention with unnecessary detail.
FIG. 1 illustrates, in simplified fashion, a typical video editing system to which the present invention is applicable. Digitally compressed video data comprising source material for use in the editing process is stored in video storage unit 10.
Overall operation of the video editing system is controlled by computer 12, which retrieves, stores and formats data stored in unit 10. The editor is provided a keyboard to control the various editing functions. Source material and edited material are displayed on one or more display units 16. A non-linear editing system embodying the present invention is the ASC VR® NLE Editor manufactured by ASC Audio Video Corporation, the assignee of this application.
FIG. 2 illustrates a typical prior art video editing keyboard. Although arranged in a conventional QWERTY layout, the keys are uniquely assigned to various 20 video editing functions. The key assignments have, in large part, become industry conventions. On the illustrated keyboard, it will be observed that the "A", "S", "D", "F" and "G" keys are employed to designate respective video tape recorders (VTR's).
Referring now to FIG. 3, a keyboard for an improved video editing system in accordance with the present invention is illustrated. Eight of the home row keys, namely, "D", "F", "G", "H", "J", "K", "L" and ";"are assigned to respective pairs of video clips, each of which has a numeric designation. For example, the "D" key is employed to designate video clip 1 or, if the shift key is also actuated, to designate video clip 9. Likewise, the "F" key is used to designate video clip 2 or 10, etc. By operation of these keys, digital video source material may be immediately brought to the source side of an edit screen where video and audio material will be evaluated for inclusion in an edit.
Up to sixteen video clips may be brought into a pre-cue buffer status by selection into an editing screen labeled "Selected Clips". These represent the "most relevant clips" for a given edit or series of edits. The system allows these "most relevant clips" to be selected by database sorting or by manual execution. Each clip of these 16 is now directly accessible by one keystroke, and they are immediately visible in a 16-shot visual full-screen grid to allow easy identification and selection.
Further, the application of this buffer status allows these clips may be placed into a "Master/Slave" relationship, allowing assignment of one clip to be the reference "Master" and all other 15 of the 16 clips to be "Slaves". The movement of up to 15 clips is made to mimic the movement of the original "Master" clip.
Selection and specification of the "Master" clip is directly mapped to the QWERTY keyboard using the present invention. By, for example, selecting clip number six on the home row of keys, this clip is assigned "Master" status for all other clips to follow, whenever the Master/Slave mode is engaged. This procedure is considered to be a major improvement in operational speed when compared to any other system.
Where there are more than 16 clips under consideration for a given edit, the "clip number" assigned by the system can also be used to select material into the edit source window, and, onto the top of the list of those clips being considered for a given edit. Selection of these clips into the 16-shot "most relevant clips" screen is accomplished by simple numerical identification of the clip desired. Such selection of "most relevant clips" may also be accomplished by using a database search.
It will be recognized that the above described invention may be embodied in other specific forms without departing from the spirit or essential characteristics of the disclosure. Thus, it is understood that the invention is not to be limited by the foregoing illustrative details, but rather is to be defined by the appended claims.
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A method and apparatus for quickly accessing and technically organizing nonlinear digital video clips for purposes of editing, processing or playback using directly-mapped keyboard assignments. Video clips are directly mapped to individual keys of a conventional QWERTY keyboard. A selected video clip is accessed and brought into the "source" side of the editing system via a single keystroke.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. provisional application 61/483,321 filed May 6, 2011 entitled “Infusion Line Management Apparatus and Method” hereby incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
The present invention relates to systems for intravenous (IV) administration of drugs and in particular to a system allowing the delivery of multiple IV solutions to a patient.
At times it is desirable to deliver to a patient multiple solutions or medications including a primary solution and a secondary solution. In such circumstances, IV bags containing the primary solution and the secondary (“piggyback”) solution may be joined with a Y-connector and a tube from the Y-connector connected to an infusion pump. The infusion pump may include, for example, a peristaltic pump element controllably pumping the solution to the patient as well as pressure sensors for sensing occlusion and the like as well as air-in-line sensors such as may detect bubbles in the fluid.
Preferential delivery of the piggyback solution may be obtained by elevating the IV bag containing the piggyback solution above that which contains the primary solution. The infusion pump will pump material from the bag at the higher elevation.
SUMMARY OF THE INVENTION
The present inventor has recognized a number of problems that can occur when administering multiple fluids using an IV pump as described above. First, at some pump rates, solution may be pulled both from the primary and secondary IV bags despite the higher elevation of the secondary bag. Second, in the event of an infusion pump failure, gravity feeding of the materials from the primary and secondary bag may occur at a higher than desired flow rate.
The present invention addresses these problems by providing a line management apparatus connectable to a primary and secondary IV bag for monitoring flow rate and independently controlling flow through the separate tubes leading to each of the primary and secondary IV bags. By monitoring flow and pinching off one of the tubes, a switchover between bags may occur only after the secondary bag is depleted as sensed by flow. Flow monitoring also allows detection of an infusion pump failure and controlling the flow rate independently of the infusion pump. In this regard, the present invention can also be used as a highly precision gravity flow infusion system. Finally, during switchover, a signal can be provided to the operator positively signaling the switchover has occurred, therefore providing convenience if immediately adding a different piggyback solution is desired.
Specifically then the present invention provides an IV line management apparatus for intravenous administrations of multiple solutions having a housing for receiving a piggyback tubing assembly comprising a primary IV tube from a primary solution IV bag as joined to a secondary IV tube from a secondary IV solution bag with a manifold connector (for example, a Y-connector or multi-way connector) and an exit tube passing from the manifold connector. First and second metering clamps engage the primary IV tube and secondary IV tube respectively when the piggyback tubing assembly is received within the housing for controlling flow through the primary IV tube and secondary IV tube according to electrical signals received by the first and second metering clamps, and at least one flow rate sensor senses flow through the tubing assembly. A controller comprising an electronic computer executing a stored program receives at least one signal from at least one flow rate sensor and provides electrical signals to the first and second metering clamps according to the stored program.
It is thus a feature of at least one embodiment of the invention to provide superior management of piggyback IV administration by allowing independent control of the streams from two IV bags.
The electronic computer may execute the stored program to control the first or second metering clamps to limit flow through the flow rate sensor to a predetermined maximum value.
It is thus a feature of at least one embodiment of the invention to provide a backup for limiting fluid flow in the event of an infusion pump failure.
The electronic computer may execute the stored program to provide electrical signals to the first and second electrical metering clamps in a first state to stop flow through the primary IV tube while allowing flow through the secondary IV tube until a flow rate lower than a second predetermined value is detected, and then to provide electrical signals to the first and second electrical metering clamps in a second state to stop flow through the secondary IV tube while allowing flow through the primary IV tube.
It is thus a feature of at least one embodiment of the invention to provide for automatic switchover between solution bags preventing flow from both bags simultaneously.
The IV line management apparatus may further include an alarm annunciator for indicating a transition between the first and second states.
It is thus a feature of at least one embodiment of the invention to positively signal a depletion of the secondary solution.
The first and second metering clamps may provide opposed jaws fitting about the primary IV tubing and secondary IV tubing and the electrical signals to the first and second metering clamps may control a separation of the jaws in pinching off the primary IV tubing or the secondary IV tubing.
It is thus a feature of at least one embodiment of the invention to provide a system for controlling fluid flow in separate IV lines that maintains a sterile envelope around the IV solution.
The electrical signals to the first and second metering clamps may control a separation of the jaws in pinching off the primary IV tubing or the secondary IV tubing to multiple different separations within a range of separations to provide control between a fully open and fully closed separation.
It is thus a feature of at least one embodiment of the invention to provide the ability to meter fluid as well as to shut fluid flow off.
The IV line management apparatus may include electrical switch operators positioned on the housing near the primary IV tubing and secondary IV tubing wherein the controller executes a stored program to respond to an operator actuation of a switch operator near one of the primary IV tubing and secondary IV tubing to cause a pinching off of alternate ones of the primary and secondary IV tubes depending on the operator actuated.
It is thus a feature of at least one embodiment of the invention to provide a simple method of designating a source of fluid flow.
The IV line management apparatus may include display elements positioned on the housing near the primary IV tubing and secondary IV tubing and communicating with the controller to indicate a state of flow through the primary IV tubing and secondary IV tubing.
It is thus a feature of at least one embodiment of the invention to provide a simple method of monitoring two different fluid flows.
The IV line management apparatus may include display elements that may be colored lights indicating a state of flow as one of open, closed, or metered and further may provide the colors and organization of a standard traffic light.
It is thus a feature of at least one embodiment of the invention to provide a simple intuitive display of multiple states of flow for different IV lines.
The IV line management apparatus may further include additional sensors sensing solution in the primary and secondary IV tubing, the sensors selected from the group consisting of air-in-line sensors, pressure sensors, and tubing-in-place sensors.
It is thus a feature of at least one embodiment of the invention to permit the line management apparatus to be used as a precise gravity feed IV system without an infusion pump.
One embodiment of the flow rate sensor is infrared sensor sensing drips passing through a drip chamber.
It is thus a feature of at least one embodiment of the invention to permit use with a variety of flow sensing techniques.
The housing may include a cover closing over the piggyback tubing assembly when received within the housing to retain the tubing within the housing.
It is thus a feature of at least one embodiment of the invention to provide a positive retention of the piggyback tubing assembly that preserves its integrity and engagement in the housing.
The cover may include a window positioned to allow visual inspection of the tubing.
It is thus a feature of at least one embodiment of the invention to provide the ability to continuously visually monitor the piggyback tubing assembly.
The IV line management apparatus may further include a lock for holding the cover closed against the housing.
It is thus a feature of at least one embodiment of the invention to permit a tamperproof control of multiple IV lines.
It should be understood that the invention is not limited in its application to the details of construction and arrangements of the components set forth herein. The invention is capable of other embodiments and of being practiced or carried out in various ways. Variations and modifications of the foregoing are within the scope of the present invention. It also being understood that the invention disclosed and defined herein extends to all alternative combinations of two or more of the individual features mentioned or evident from the text and/or drawings. All of these different combinations constitute various alternative aspects of the present invention. The embodiments described herein explain the best modes known for practicing the invention and will enable others skilled in the art to utilize the invention.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a simplified perspective representation of an example line management apparatus per the present invention used in conjunction with a piggyback tubing assembly and an infusion pump;
FIG. 2 is a front elevational view of the line management apparatus of the present invention with the cover open showing various sensors, actuators, displays and annunciators;
FIG. 3 is a block diagram of the principal elements of the pump including a processor for monitoring the sensors of the present invention using a stored program and for controlling actuators;
FIG. 4 is a cross-sectional view of metering clamp actuators showing their operation on a contained tubing element;
FIG. 5 is a fragmentary front elevational cross-sectional view through a flow rate sensor having a chamber providing falling drops positionable between capacitor plates flanking the flow rate sensor chamber when the flow rate sensor chamber is inserted into the pump;
FIGS. 6 a and 6 b are a fragmentary front cross-sectional view and a top plan cross-sectional view, respectively, of a second embodiment of the flow rate sensor providing a chamber with a contained turbine wheel and flanking capacitive sensors when the flow rate sensor chamber is inserted into the pump;
FIG. 7 is a simplified flowchart of a program executing on the processor FIG. 3 ; and
FIG. 8 is a figure similar to FIG. 2 showing an embodiment using a multi-way connection system.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1 , a line management apparatus 10 of the present invention may receive IV lines 12 and 14 from a primary IV bag 16 and a secondary (“piggyback”) IV bag 18 through a top surface of the line management apparatus 10 . Generally the secondary IV bag 18 may be mounted higher than the primary IV bag 16 on an IV pole 19 ; however, this is not required in the present invention. The IV lines 12 and 14 may be joined by a Y-connector 20 leading to an outlet line 22 , the latter of which may be received by a standard infusion pump 24 . Generally the IV lines 12 and 14 , Y-connector 20 , and outlet line 22 provide a piggyback tubing assembly 25 .
The infusion pump 24 , as is understood in the art, provides a peristaltic pump element that accurately meters liquid through the outlet line 22 and to a needle 26 or the like that may be inserted into a patient (not shown). As is understood in the art, the infusion pump 24 may further provide sensors such as air-in-line sensors and pressure sensors for monitoring the flow through outlet line 22 and a tubing in-place sensor for ensuring the tubing of outlet line 22 is properly seated in the pump 24 . The infusion pump 24 may further provide for a time control of the flow through outlet line 22 as well as alarms indicating problems with that flow.
Referring now to FIG. 2 , the line management apparatus 10 may provide for a housing 30 having a front face 32 that may receive the piggyback tubing assembly 25 within channels and sockets in the front face 32 . In particular, each of the IV lines 12 and 14 may pass downward through left and right air-in-line sensors 33 , left and right tubing loaded sensors 34 , and left and right metering clamps 36 .
The air-in-line sensors 33 may consist of two ultrasonic transducers: one serving as an actuator to convert electrical energy into mechanical energy, and the other serving as a receiver to convert mechanical energy into electrical energy. In one embodiment, the actuator is implemented with a piezoelectric actuator. When an electrical signal is applied to the piezoelectric actuator, cyclic deformation of piezoelectric material inside the actuator produces a stress wave that travels across the tubing of IV lines 12 and 14 . Due to the significant difference of attenuation factor from liquid to air, the stress wave detected by the receiver varies significantly depending upon whether liquid or air is within the tubing adjacent to the receiver. Therefore, air can be differentiated from liquid, and an indication of the presence of air bubbles or line empty state may be made.
The tubing-loaded sensors 34 detect the presence of tubing of IV lines 12 and 14 and outlet line 22 properly seated in the channels in the housing 30 . The seated tubing can be with or without liquid in it. In one embodiment, the tubing-loaded sensors 34 consist of a magnet and a Hall sensor. When tubing is loaded, the magnet is pushed closer or father away from the Hall sensor, depending upon the chosen implementation. Therefore, the signal obtained from the Hall sensor can be used to determine whether the tubing is loaded. In another embodiment, the tubing-loaded confirmation sensor consists of a LVDT (Linear Variable Displacement Transducer). When a tube is loaded, movement of the ferromagnetic core results in a transducer voltage change due to mutual inductance change. The resulting voltage is used to determine the tubing loading condition. In another embodiment, the tubing loading condition can be determined by analyzing a signal from the air-in-line sensor 33 receiver due to observable differences among tube not loaded, empty tube, and liquid filled tube states.
An upstream occlusion condition can also be detected by the same type of sensors that detect the presence of tubing.
Positioned below the metering clamps 36 are the operators of left and right electrical switches 38 , and left and right indicator banks 40 , each positioned near a respective IV line 12 and 14 to be clearly associated with one of those IV lines 12 and 14 . Each indicator banks 40 may comprise three LEDs providing red, yellow, and green lights and ordered from top to bottom in the manner of a standard traffic signal to accommodate a color blind user. The LEDs may indicate conditions such as liquid flowing, standby (tubing filled with liquid, but liquid is not flowing), or no flow (no tubing loaded, air in tubing, or tubing closed by flow regulator).
Outlet line 22 leading from the Y-connector 20 passes through a flow rate sensor 42 after which outlet line 22 may exit the line management apparatus 10 .
The front face 32 also provides a baffle for a speaker 44 . The speaker 44 can be used to generate an alarm sound when a preset condition is met, such as flow rate out of range, line empty/air in line, tube not loaded, both line switches at off position when flow is expected, as well as for other conditions that will be described below.
A screen 46 for displaying alphanumerics or text may also be provided, for example, to indicate flow rate. Line condition can also or alternatively be indicated by the screen 46 which may be provided as an LCD, LED or other commonly known type of display screen.
The housing may further provide a support tab 48 at its top edge for attachment to the IV pole 19 and may have a hinging cover 50 pivoting about one vertical edge of the housing 30 to open and close over the front face 32 of the housing 30 . The cover 50 may provide for a central transparent window 52 and a lock hasp 54 engaging with a corresponding lock hasp 56 on the housing that allows locking of the cover 50 in a closed position on the housing 30 . When the cover 50 is closed over the front face 32 , it retains the piggyback tubing assembly 25 therein and the window 52 allows visual inspection of each of the elements on the front face 32 .
Referring now to FIG. 3 , the line management apparatus 10 may include a controller 60 (which may be a processor 61 based system) having a memory 62 for holding a stored operating program and data 64 controlling operation of the line management apparatus 10 as will be described below. In particular, the controller 60 may use the data in the memory 62 to control metering clamps 36 to ensure the desired dose and delivery rate to the patient. The controller 60 may further communicate with the flow rate sensor 42 of the present invention for receiving a signal therefrom as will be described. Further, the controller 60 executing the stored program 64 may read a signal from the air-in-line sensors 33 and the tubing loaded confirmation sensors 34 .
Referring still to FIG. 3 , the controller 60 may also communicate with a screen 46 for displaying and/or inputting various programming and operating parameters, a speaker associated with speaker 44 for providing audible alarm signals, and switches 38 for inputting data to the controller 60 , for example, for selecting among solution delivery through IV lines 12 and 14 . The controller 60 may also provide for signals to the indicator bank 40 to control their illumination. This communication may be through standard interfaces 70 understood in the art Referring now to FIG. 4 , the metering clamps 36 may provide for opposed stationary jaw 72 and movable jaw 74 that may flank each of IV lines 12 and 14 . Movable jaw 74 may communicate through a lead screw 76 with a motor 78 , for example a servo or stepper motor, that may rotate the lead screw 76 to move the jaws 72 and 74 to various degrees of separation. As such, the jaws 72 may close to fully block flow through the IV lines 12 and 14 , or open fully for free flow through IV lines 12 and 14 or may be positioned in between open and closed to provide for a metering of flow. In an alternative embodiment, where only full or no flow is required, the metering clamps 36 may be actuated by solenoids replacing the servo or stepper motors.
Referring now to FIG. 5 , in the first embodiment of the invention, the flow rate sensor 42 may provide for a generally cylindrical housing 82 receiving a flexible tube of the IV line 12 or 14 and having a diameter substantially larger than the diameter of the tube of IV lines 12 and 14 . A connection between the tube and the housing 82 provides an orifice opening into an air space 84 , the orifice forming liquid from the IV bag 16 or 18 into drops 86 that may fall through the air space 84 into a pool 89 at the bottom of the cylindrical housing 82 . The pool 89 may communicate with a second tube providing a drain therefrom and a continuation of the IV line as outlet line 22 .
When the flow rate sensor 42 (formed with the piggyback tubing assembly 25 ) is placed within a socket in the front face 32 of the housing 30 , it will be flanked by first and second plates 90 a and 90 b positioned across a diameter of the cylindrical housing 82 and accordingly across the air space 84 . Drops 86 passing through the air space 84 thereby create a change in capacitance between the plates 90 a and 90 b caused by the increased dielectric constant of the material of the drop 86 . For example, the dielectric constant of water is approximately 34 to 78 times that of air. This capacitance may be measured by a number of techniques including, for example, measurement of changes in a frequency of the oscillator incorporating the capacitance between the plates 90 a and 90 b into a resonant circuit or by use of the capacitance between plates 90 a and 90 b as part of an integrator and measuring a time constant of a ramping up of the integrator after periodic reset. These fluctuations in capacitance may be used to count the drops 86 and deduce a flow rate. Alternatively an infrared light beam may be used to count drops in the situation.
Referring now to FIGS. 6 a and 6 b , in a second embodiment the flow rate sensor 42 may also provide for a cylindrical housing 100 . In this case the cylindrical housing 100 holds suspended therein a free spinning turbine 102 having a rotational axis 104 generally along the direction of flow and along the axis of the cylindrical housing. The cylindrical housing 100 may be attached at its upper and lower ends to outlet line 22 leading from the Y-connector 20 to be placed in series with the outlet line 22 . Generally, the turbine 102 provides for one or more canted blades 106 having a known pitch to cause a predetermined rotational rate of the turbine 102 with flow of the liquid within the cylindrical housing 100 along axis 104 .
Plates 90 a and 90 b may flank the cylindrical housing 100 when the flow rate sensor 42 is placed within the socket in the front face 32 of the housing 30 as described above with respect to the embodiment of FIG. 5 . One or more blades 106 of the turbine 102 may include high conductivity or dielectric inclusions 108 , for example aluminum inserts or metal plating, that change the effective spacing of the capacitor plates 90 a and 90 b with rotation of the turbine 102 . Alternatively, the dielectric material of the turbine blade 106 may provide for the necessary variations in capacitance between the plates 90 a and 90 b causing a variation in capacitance as a function of rotation of the turbine 102 . It will be understood that the change in capacitance signal between the plates 90 a and 90 b may be used to deduce rotation of the turbine 102 and thus the total flow of liquid through the outlet line 22 . It will be appreciated that other sensing techniques such as Hall effect sensing may also be used.
Although two flow rate sensors have been described above, it will be appreciated that other flow rate sensors may also be used in this capacity including, for example, thermal time of flight sensors, ultrasonic sensors and the like.
For example, in another embodiment, the flow rate sensor 42 for outlet line 22 may consist of an ultrasonic flow meter and the supporting circuits. The ultrasonic flow meter may have two piezoelectric transducers and a tubing section between the two transducers. Mechanical stress waves can be generated by applying an electrical signal to either transducer. Velocity of stress wave propagation along and against the flow direction within the tube is affected by the velocity of the liquid. By knowing the cross section of the tubing section and the length of the tubing section, flow rate can be calculated using time difference between the stress wave propagation directions.
In another embodiment, the flow rate sensor 42 for the outlet line 22 may consist of a laser based flow meter and the supporting circuits. Liquid inside a tubing section with a specific cross section can be heated with a heating laser, and the change in fluid reflectivity and/or diffractivity due to added thermal energy can be utilized to measure flow rate. The change in reflectivity and/or diffractivity can be detected by a sensing laser, photo diode, and corresponding optical components such as mirrors and apertures.
In another embodiment, the flow rate sensor 42 for the outlet line 22 may consist of a thermal time-of-flight based flow meter and the supporting circuits. Fluid flowing through the tubing is heated up by a certain amount of thermal energy. A thermal probe(s) at a downstream location measures the temperature change of the fluid. The flow rate can be calculated from temperature change data.
In another embodiment, the flow rate sensor 42 for the outlet line 22 may consist of two pressure sensors and the supporting circuits. The two pressure sensors are positioned at a certain distance along the flow direction. Differential pressure can be calculated from pressure values measured by the two pressure sensors. By knowing the cross section of the tubing, distance between two differential pressure sensors, and the differential pressure, flow rate can be calculated. Any of various pressure sensors known to one skilled in the art may be employed.
In another embodiment, the flow rate sensor 42 for the outlet line 22 may be a differential pressure sensor, using a piezoresistive monolithic silicon pressure sensor and supporting circuitry. Commercially available piezoresistive sensing element (such as part #MPVZ4006G from Freescale Semiconductor, Inc) can be utilized to sense the differential pressure at two different locations along the flow direction. Deformation of the diaphragm results in resistance change, which can be used to directly calculate the differential pressure. Once differential pressure is obtained, with known cross section of tubing and distance between two pressure ports along the line, flow rate can be measured.
Referring now to FIGS. 1, 3 and 7 , the program 64 executed by the processor 61 , as indicated by process block 110 , may receive a state setting by the user indicating in which of IV lines 12 and 14 initial flow is desired. The state setting signal may come from switches 38 which when pressed indicate that the IV line 12 or 14 closest to the switch 38 is to be the line that will have flow and the remaining line will be clamped off for no flow by adjustment of the appropriate metering clamps 36 . At this time, indicator bank 40 shows a green light if flow is occurring in the particular tube and a red light if no flowing is occurring.
As indicated by decision block 112 , as material flows through outlet line 22 , the flow is monitored by flow rate sensor 42 to make sure it is below a predetermined limit that should be provided to the patient. This first predetermined limit enforces a degree of safety in the event that the infusion pump 24 fails in an open state or may be a routine monitoring used when the line management apparatus 10 is used without an infusion pump 24 .
If the flow exceeds the indicated limit, then the processor 61 may close the metering clamp 36 associated with the active IV line 12 or 14 as indicated by process block 114 and provide an output alarm as indicated by process block 116 . The alarm will typically be an audible alarm demanding immediate attention.
When the line management apparatus 10 is being used without an infusion pump 24 , then instead, at process block 118 , the metering clamp 36 associated with the open IV line 12 and 14 may be tightened down until proper flow rate is obtained. This metering is indicated by a green or yellow illumination in the corresponding indicator bank 40 and provides closed loop regulation of flow in conjunction with flow rate sensor 42 .
If the first predetermined flow rate limit has not been exceeded at decision block 112 , then at decision block 120 it is determined whether the active IV line 12 or 14 has a flow below a second predetermined limit indicating depletion of the solution in the associated IV bag 18 or 16 . If this second predetermined flow limit is not maintained, then the program 64 moves to process block 122 and a state-switch occurs in which the open IV line 12 or 14 is fully closed (typically the IV line 12 associated with the piggyback solution) and the other IV line 12 or 14 (typically the primary IV line 14 ) is opened. In this case a visual alarm may be output indicating to a healthcare professional that the secondary solution from IV bag 18 has been exhausted.
Referring now to FIG. 8 , it will be appreciated that the principles of the present invention, as described above, may be extended to a system having additional inlet IV lines beyond primary IV line 12 and secondary IV line 14 , for example, to provide for a tertiary IV line 12 ′, and optionally a quaternary IV line 14 ′ and possibly additional IV lines joined by a manifold connector 20 ′ merging the flows from these multiple inlet IV lines into the single outlet line 22 . In this case the air-in-line sensors 33 , tubing loaded sensors 34 , metering clamps 36 , switches 38 and indicator banks 40 may be duplicated for each of these inlet IV lines to provide independent sensing and control of each line.
Such multi-way systems may be desirable for anesthesiology where additional medications and materials need to be simultaneously administered in a controlled fashion to a patient. Such multi-way systems may also be desirable for staging multiple bags of medications for sequential delivery and may operate, for example, to allow the flow through one inlet IV line at a time until a flow rate drop below a predetermined amount, and then to switch to the next IV line in a predetermined sequence. Generally, it is contemplated that the invention may provide for a wide range of different inlet IV line numbers ranging from 2 to 8 and thus including two inlet IV lines, greater than two inlet IV lines, greater than three inlet IV lines, etc. The extension of the circuitry of FIG. 3 to include additional control lines will be understood from this disclosure to those of ordinary skill in the art.
Certain terminology is used herein for purposes of reference only, and thus is not intended to be limiting. For example, terms such as “upper”, “lower”, “above”, and “below” refer to directions in the drawings to which reference is made. Terms such as “front”, “back”, “rear”, “bottom” and “side”, describe the orientation of portions of the component within a consistent but arbitrary frame of reference which is made clear by reference to the text and the associated drawings describing the component under discussion. Such terminology may include the words specifically mentioned above, derivatives thereof, and words of similar import. Similarly, the terms “first”, “second” and other such numerical terms referring to structures do not imply a sequence or order unless clearly indicated by the context.
When introducing elements or features of the present disclosure and the exemplary embodiments, the articles “a”, “an”, “the” and “said” are intended to mean that there are one or more of such elements or features. The terms “comprising”, “including” and “having” are intended to be inclusive and mean that there may be additional elements or features other than those specifically noted. It is further to be understood that the method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also to be understood that additional or alternative steps may be employed.
References to “a microprocessor” and “a processor” or “the microprocessor” and “the processor,” can be understood to include one or more microprocessors that can communicate in a stand-alone and/or a distributed environment(s), and can thus be configured to communicate via wired or wireless communications with other processors, where such one or more processor can be configured to operate on one or more processor-controlled devices that can be similar or different devices. Furthermore, references to memory, unless otherwise specified, can include one or more processor-readable and accessible memory elements and/or components that can be internal to the processor-controlled device, external to the processor-controlled device, and can be accessed via a wired or wireless network.
It is specifically intended that the present invention not be limited to the embodiments and illustrations contained herein and the claims should be understood to include modified forms of those embodiments including portions of the embodiments and combinations of elements of different embodiments as come within the scope of the following claims. All of the publications described herein, including patents and non-patent publications, are hereby incorporated herein by reference in their entireties.
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A line management apparatus for managing multiple IV lines connected in a Y fitting provides for flow sensing and for electronic control of flow in the multiple lines. The line management apparatus may be used independently as a precise gravity feed IV system or may provide for use in combination with an infusion pump to ensure proper delivery of multiple solutions without blending of the multiple solutions.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of U.S. application Ser. No. 14/148,673, filed Jan. 6, 2014 (U.S. Pat. No. 9,313,626 to be issued Apr. 12, 2016), which is a continuation of U.S. application Ser. No. 13/898,442, filed May 20, 2013, now U.S. Pat. No. 8,624,718, which is a continuation of U.S. application Ser. No. 13/540,592, filed Jul. 2, 2012, now U.S. Pat. No. 8,446,270, which is a continuation of U.S. application Ser. No. 12/470,857, filed May 22, 2009, now U.S. Pat. No. 8,212,661, which claims priority to U.S. provisional application Ser. No. 61/055,290, filed May 22, 2008, which are hereby incorporated by reference in their entireties.
BACKGROUND
[0002] 1. Field
[0003] This application relates to mobile telephones and other mobile portable communications devices, and to controlling the alert signal for such devices.
[0004] 2. Description of Related Art
[0005] Portable cellular telephones and handheld messaging devices generally include one or more transducers to provide audible, tactile or visible alert signals indicating various forms of incoming messages. Incoming messages may include, for example, live telephone calls, voice messages, electronic mail, and text messages. Users generally carry such portable phones and messaging devices on their person for much or all of the day, and consequently distracting alert signals may be emitted by the portable device at inappropriate times. Portable messaging systems often provide a means for disabling any desired alert signal, but these means require the user to manually disable the alert signal via a switch or user input command. Likewise, re-enabling the alert signal generally requires manual input. Users may find it inconvenient or difficult to consistently deactivate and reactivate the alert signal using a manual control means.
SUMMARY
[0006] The present technology provides for automatic control of an audible alert signal for a portable messaging device, based on priority information determined from the incoming message. The control may include controlling a quality of the alert signal based on the priority information, or disabling the alert signal entirely if the priority information falls below a threshold.
[0007] This technology also provides for automatic disabling and re-enabling of an alert signal for a portable messaging device, in response to sensory input collected by a sensor in communication with the messaging device. The sensor may be physically near the messaging device, connected to the messaging device via a suitable interface, incorporated into the same housing as the messaging device, or any combination of the foregoing. For example, a GPS sensor or other locating system may be integrated into a portable messaging device configured to respond to sensor input to determine, in conjunction with governmental, system operator, sender, or end user defined parameters, when the messaging device emits an alert signal as notification of incoming or received messages.
[0008] For example, when a cellular phone or other portable device receives sensor input indicating that it is in motion at a speed greater than a preset limit, or has recently been in such motion within a set time period, message delivery (or, alternatively, notice that a message has been delivered) may be delayed until such time that the device is not in motion (or has been not in motion for a set time period). In this manner, alert signal notification of inbound messages, phone calls, emails, SMS texts, or even pre-set alarms (such as an internally entered appointment reminder on the device) are delivered to the user in a manner that does not impair safety. Optionally, this setting may be changed by the user when the user is able to deal with such messages safely despite being in motion, such as when the user is a passenger in a vehicle, not the driver. In addition, the device may utilize location or motion information transmitted from the vehicle, may utilize data as to the cellular tower and distance from the tower (and increasing or decreasing signal strength indicating movement toward or away from a tower), or the fact that it is “paired” with a vehicle sound system (as via Bluetooth™) to indicate motion or potential motion.
[0009] A threshold may be defined requiring motion greater than a certain speed, with operating logic to ensure that motion under, for example, 5 miles per hour, is not sufficient to trigger disabling of the alert signal. Likewise, when motion drops below a predetermined threshold the alert signal may be re-enabled. So as an example, a user driving at 5 miles per hour has a portable messaging device (PMD) that works normally, but when he exceeds 5 miles per hour the PMD may sense this and switch to a mode where all alerts other than phone calls (or even including phone calls) are silenced until the vehicle reaches a speed under 5 miles per hour again.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The present invention, in accordance with one or more various embodiments, is described in detail with reference to the following figures. The drawings depict embodiments of the invention, by way of example.
[0011] FIG. 1 shows an example of a portable messaging device with alert signal control means.
[0012] FIG. 2 shows an example of a system using an automobile and wireless transmitter for alert signal control.
[0013] FIG. 3 shows a method 300 for controlling alert signaling in a portable messaging device.
DETAILED DESCRIPTION
[0014] FIG. 1 shows an exemplary portable messaging device 100 including familiar interface components such as a display screen 102 , keypad 104 , microphone 106 , audio transducer 108 and housing 110 sized for handheld use. A circuit 112 (shown schematically) may be enclosed in the housing 110 .
[0015] Circuit 112 may comprise various components in electronic communication with one another, including a cellular transmitter/receiver 114 connected to a central processor 116 . CPU 116 may be connected to receive input from the keypad, microphone, or other input device, and operates system and application software stored in system memory 118 . CPU 116 , either directly or via an interface circuit (not shown) may drive an audio output transducer 120 for outputting an alert signal and/or audio message content. Other output signaling devices may also be used, such as a mechanical vibrator for outputting a tactile alert signal or a signal light, such as one or more L.E.D.'s, for providing a visual alert. The display 102 may also be used to provide a visual alert signal. The CPU, memory, and cellular transmitter/receiver may be considered core components for performing primary communication functions of device 100 .
[0016] Circuit 112 may further comprise ancillary components for performing sensing functions, or for communicating with an external sensor. By way of example, two such components are shown, a wireless frequency-hopping spread spectrum (e.g., Bluetooth™) module 122 for communicating with external Bluetooth-enabled devices, and a Global Positioning System (GPS) receiver for determining geographical location. Either or both of these components may be used. In this disclosure, embodiments using GPS or Bluetooth™ modules are discussed in more detail, but the technology is not limited thereby. Other useful sensors may include a light sensor, enabling automatic control of the alert signal responsive to external impinging light levels or temporal patterns, or a microphone for enabling similar control in response to external sound levels and patterns. Circuit 112 may also include a system clock or timer for measuring a current time, or elapsed time.
[0017] Alert signal control as described herein should be distinguished from command-based control. The Bluetooth™ unit 122 , the GPS receiver 124 , and other input sensors (if used) are not used merely for command control of the auto-disable feature. Instead, sensors are used for determining a present environmental status of the mobile device, and then decision logic is applied using the CPU in response to sensor input, to determine how alert signals for incoming messages should be controlled. Therefore, the portable device 100 responds differently to incoming messages depending on an external measured environmental state that is determined without command input. Of course, the use of environmental-based alert signal control need not exclude command-based control, of which complementary use may often be desirable. For example, circuit 112 may be configured to permit configuration of an auto-alert disable system in response to user command input.
[0018] One environmental variable of interest in alert signal control may include velocity. It may be desirable to mute (disable) the alert signal when the phone is moving at greater than a specified speed. A current velocity may be easily determined by reference to a GPS receiver and a system clock or timer. Other methods of determining location may also be suitable, such as by triangulation from any other known transmitters that make up a cellular network. However with present technology GPS locating is both accurate and relatively inexpensive, and may provide a suitable means for determining the mobile device's present location.
[0019] In lieu of an internal GPS receiver 124 , device 100 may obtain its location and/or speed from any external source. This may be conveniently accomplished via a Bluetooth™ transmitter/receiver as currently implemented in many cellular phones. Circuit 112 may periodically scan for an authorized external Bluetooth™ signal to obtain environmental data. For example, a Bluetooth™ transmitter/receiver 202 may be integrated into the electrical system of an automobile 200 , as shown in FIG. 2 . As such, the device 100 may have access to GPS location data via a GPS receiver installed or located in the automobile. Device 100 may also receive current velocity information from the speedometer of car 200 via the Bluetooth™ interface 202 . Use of Bluetooth™ is merely exemplary, and alternative communication standards may also be used, including but not limited to wired or wireless standards such as USB, wireless USB, Zigbee™ and UWB.
[0020] Device 100 may also determine its relative location inside car 200 via the Bluetooth™ component 202 or other transmitter. For example, relative signal strength or triangulation may be used within the car interior, if so equipped. In the alternative, the car 200 or device 100 may be configured to ask the user where in the car the phone is located, in response to detecting that it has entered into the vehicle. For example, when a user carrying device 100 enters car 200 , the presence of the phone may be detected and an onboard computer may output a verbal question such as “Is John a driver or passenger?” to which the user may reply “passenger” or “driver” as the case may be. The onboard computer may inform device 100 of the response to the query. The mobile device 100 may control the alert signal in accordance with the received response, for example, by disabling the alert signal on a speed-sensitive basis only if the response or other sensor data indicates that the mobile device is being used by the driver. The driver will therefore not be distracted by alert signals from device 100 while driving the car above a defined threshold speed, which may be any number of zero or greater.
[0021] Device 100 may also consider message parameters when determining whether to disable alert signaling. For example, certain message senders may have a capability to mark some messages or incoming calls as “urgent.” Device 100 may be configured to selectively disable alert signals for incoming messages that are not marked as “urgent” by an authorized sender, while providing alert signals for urgent messages regardless of sensor input, or only in a narrower range of environmental conditions. For example, device 100 may provide alert signals for “urgent” marked messages while moving up to speeds of 60 miles per hour and for all other messages while moving up to five miles per hour.
[0022] Use of a self-contained locating and velocity-measuring system in device 100 may be advantageous for other reasons. For example, a portable communication device equipped with a GPS locating system may provide various location-based services, including navigational guidance and location-specific advertising. Use of the GPS system for velocity determination in such a GPS-equipped device may be merely incidental, and therefore may add negligible cost to the device.
[0023] FIG. 3 shows a method 300 for controlling alert signaling in a portable messaging device, such as may be performed using software or firmware operating in a device as described herein. Method 300 represents a performance loop that may be initialized shortly after powering up the device. A computer-readable medium may be used to store program instructions, that when executed by a processor of the portable messaging device, cause the device to perform as described herein below. After the loop is initialized, the device may scan for input 302 to one or more ports capable of receiving sensor (e.g., GPS) input. Scanning may be done periodically, and/or in response to an interrupt originating from a sensor device. In the alternative, or in addition, the device may periodically request sensor input from a connected sensor, which may respond to the device's requests with sensor data. The device may also wirelessly broadcast a query signal seeking a response from any sensors that may be available in the immediate area.
[0024] After scanning for incoming sensor data, the device may receive and process sensor data 304 . The sensor data may be time stamped and held in a memory of the device for later use. In the case of velocity determination, two or more of the most recent positional sensor data (indicating a current position of the sensor) may be held in system memory. In the alternative, or in addition, the device may calculate a current velocity and store in memory. Sensor data may be processed as necessary to provide useful input for alert signal controlling. For example, a feature may be provided wherein the volume or intensity of the alert signal is modulated in response to ambient noise. The noisier the ambient environment, the louder the alert signal provided, and conversely the alert signal volume may be diminished in quieter environments. To accomplish this control, the processor may use microphone input to calculate an average noise level over a recent time slice, for example, for the most recent second or more recent ten seconds. The calculated noise level may then be stored in system memory for use in alert signal control. Similar use of sensor data may be used to silence or lower the volume of the alert signal when the environmental light levels are low.
[0025] The portable messaging device may normally be in a wait state 306 , waiting to receive an incoming message. During waiting, the device may periodically cycle through scanning, receiving and storing sensor data as described above. The wait state may be interrupted when an incoming message is received 308 . The feature of automatic signal disabling or automatic volume control as described herein may be subject to manual control, so that a user of the device may shut off this feature when it is not desired. Thus, before executing an alert signal control routine, the device may determine whether or not the automatic alert signal control feature has been temporarily turned off at 310 . If automatic control has been disabled, the device may output an alert signal 312 according to default or user-specified parameters, and dispose of the incoming message (whether phone call, text message, electronic mail, or other) in a normal fashion 314 .
[0026] If automatic control has been enabled 310 , the device may determine a most recent or a present environmental state 316 of the device by retrieving most recent stored sensor input from system memory. In the alternative, sensor input may be solicited and received in response to receipt of the incoming message 308 . Examples of environmental state may include, for example, the position and velocity of the device, acceleration of the device, ambient noise level, ambient light level, or any other sensor-based measure that may be useful for controlling an alert signal. Optionally, the device may determine a message status 318 with respect to alert signal control. Message metadata or other characteristics may indicate a special status used to modulate the alert signal, for example “message type,” (e.g., “voice call”, “e-mail” etc.) “urgent,” “normal,” or “low-priority.” Status indicators such as these may be used to determine how to control that alert signal in conjunction with the environmental indicators.
[0027] After collecting environmental and (optionally) message parameters, the portable messaging device may evaluate the parameters against defined rules to determine whether or not conditions have been satisfied 320 for providing an immediate alert signal. Various exemplary rules have been described above. For example, the alert signal may be disabled if the device is moving at greater than a threshold velocity, if the ambient light levels are too low, etc. Even an ambient temperature may be used as input to a control scheme, as it may indicate whether or not the device is being worn close to a user's body. If conditions for providing an alert signal are not satisfied, the device does not output an alert signal 322 at that time. The device may delay output of the alert signal and may hold the incoming message in a memory 324 , and wait 306 until environmental conditions change to satisfy conditions for providing an alert. Live messages such as incoming voice calls may be rolled over to voice mail while other messages may be placed in a message inbox. During a wait period, additional sensor input may be scanned for 302 or received 304 . Program execution may then loop periodically back to environmental testing 316 and 320 , so that the alert signal can be re-enabled once environmental conditions (e.g., device velocity decreased to safe level) are satisfied 320 .
[0028] If conditions for providing an alert signal are satisfied 320 , the device may determine how to modulate the alert signal 326 in response to environmental or message parameters. Different signals may be provided based on message priority type or urgency level. The volume or intensity of the alert signal may be controlled based on sensor input as previously described, for example, by changing the alert signal volume or changing the alert tone. In the alternative, the alert signal is not modulated and step 326 is omitted. The device may then output the alert signal 312 , and dispose of the message 314 in a conventional fashion.
[0029] The method 300 merely exemplifies a control scheme for controlling an alert signal in response to environmental sensor input. The present technology is not limited by this example.
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An electronic communication system provides text or voice messages to remote receiving devices, such as cell phones or PDA's. The receiving devices include a function for determining a message priority, prior to providing any audible alert signal indicating that the message is received. If an incoming message has a priority that is lower than a necessary threshold, the function prevents the audible alert signal from being generated at the time the message is received.
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BACKGROUND OF THE INVENTION
1. Field of Invention
This invention pertains to an apparatus and method for creating artwork in wax, and particularly for creating temporary wax artwork.
2. Description of the Relevant Art
There are known batik kits and heating devices. For example, Bartleson U.S. Pat. No. 3,840,113 discloses a batik kit for creating designs on fabric using wax and dyes. Bartleson, however, fails to disclose a kit or method of creating two and three dimensional temporary wax articles using a variety of wax applicator tools.
Gill et al. U.S. Des. Pat. No. 346,245 discloses the ornamental design of a commercial food cooking device. Gill, however, fails to disclose a heating unit having a plurality bins for heating articles separately, and wherein each bin is selectively removable and includes a section defined thereon for conveniently pouring a partially melted article.
Reading U.S. Pat. Des. No. 185,614 discloses a baby dish, but fails to disclose a heating unit having a plurality of removable bins for heating articles separately, and wherein each bin includes a means for conveniently pouring or discharging a partially melted article.
Wallace U.S. Pat. No. 2,166,616 discloses a paint box palette for maintaining and storing a plurality of liquids separately, but fails to disclose a device for separately heating a plurality of articles, including a plurality of detachably engageable bin members having means for discharging substantially melted materials therefrom.
SUMMARY OF THE INVENTION
The present invention overcomes the above-discussed limitations and shortcomings of known artwork creating devices and satisfies a significant need for such an apparatus which allows the user thereof to create both permanent and temporary two and three dimensional artwork utilizing wax material.
According to the invention, there is provided an apparatus for use in creating artwork in wax, comprising a heating unit having a plurality of bins defined therein, means for individually controlling the temperature of each bin, means for selectively detaching each bin from the heating unit, and wherein each bin includes a spout for pouring semi-liquid compositions; at least one trowel member having means for removing a semi-melted composition from a bin of the heating unit and means for applying a semi-melted composition to an article so as to achieve any of a wide variety of shapes and surfaces; a plurality of brushes of various sizes and shapes, for applying a substantially liquid wax compound to an object; and an applicator for dispensing a partially solidified composition in any of a plurality of shapes.
The method of creating the artwork comprises the steps of obtaining the heating unit and placing the detachable bins therein; placing the desired solid wax compounds in the appropriate bins, each bin having a wax compound of a different color; independently heating the desired bins using the temperature control means of the heating unit, until the desired consistency of each wax compound is reached; selectively removing portions of the semi-melted wax compounds from the heating bins and applying the wax portions to an object using a trowel, brush, or other applicators. After the wax compounds have hardened, the wax may be selectively removed from the object using a trowel or similar article, and placed in the appropriate bins for reuse through reheating the wax therein. When not in use, the wax compounds are optionally stored in the bins.
The method and corresponding apparatus is useful in easily creating artwork by applying the wax compounds to screen, glass or canvas. Alternatively, three dimensional artwork may be created formed substantially of wax.
It is an object of the invention to provide an apparatus and method for creating artwork in wax, for use by both children and adults.
It is another object of the invention to provide a method for creating temporary artwork so that the wax may be reused to create other wax artwork.
Another object of the invention is to provide a kit for creating such artwork in wax.
Other objects, advantages and salient features of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the annexed drawings, discloses preferred embodiments of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the heating unit of the preferred embodiments of the present invention.
FIG. 2 is a perspective view of trowel members of the preferred embodiments of the present invention.
FIG. 3 is a perspective view of brush members of the preferred embodiments of the present invention.
FIG. 4 is a perspective view of a third applicator of the preferred embodiments of the present invention.
FIG. 5 is a perspective view of bin members of the preferred embodiments of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIGS. 1-5, there is shown an apparatus for creating artwork in wax, including heating unit 1, trowel members 2-3, brushes 4, wax applicator 5-6, and removable bins 7.
Heating unit 1 is adapted to transfer heat to a wax compound, heating unit 1 having a recess defined therein and a plurality of partitions 1b defined laterally across the recess so as to form a plurality of recesses 1a, as shown in FIG. 1. The side and bottom surfaces of recesses 1a, and partitions 1b are preferably constructed from a substantially thermally conductive material so as to effectively transfer heat to articles placed therein.
Heating unit 1 additionally includes a means for independently controlling the temperature of each recess 1a. Referring to FIG. 1, such independent heat controlling means comprises temperature control dials 1c, one control dial 1c corresponding to a separate recess 1a. Each control dial 1c is preferably but not necessarily disposed adjacent its corresponding recess 1a. Markings are preferably but not necessarily printed or otherwise disposed around each dial 1c so as to indicate to the user the selected temperature setting. Whereas each dial 1c controls the heat transferred to its corresponding recess 1c, master switch 1d universally switches temperature controls to recesses 1c between an active (ON) state and an inactive (OFF) state.
Heating unit 1 is preferably but not necessarily electrically heated, using heating coils or other heat generating and transferring mechanisms. In the preferred embodiments of the invention, the outer surface of heating unit 1 is thermally is listed from recesses 1a so that heating unit 1 may rest on any surface or be handled by the user without causing any adverse effects.
The preferred embodiments of the present invention preferably but not necessarily include a plurality of bin members 7 (FIG. 5), which are each sized and shaped so as to fit substantially securely within a recess 1c of heating unit 1 so as to substantially prevent tipping. Bin members 7 are preferably constructed from a relatively thin, thermally conductive material, such as tin foil, so as to quickly transfer heat from a recess 1a to the article to be heated in bin 7.
Bin members 7 preferably but not necessarily include a means for pouring a semi-melted composition. As shown in FIG. 5, the pouring means comprises handle 7a and pouring spout 7b. Handle 7a preferably but not necessarily extends upwardly from an inner surface of the longitudinal sides of bin 7 so as that bin 7 maintains secure engagement with a recess 1a of heating unit 1 when placed therein. Handle 7a is preferably but not necessarily integrally formed with bin 7 as a unitary member, but alternatively handle 7a is selectively removable therefrom so that only one handle 7a is needed to pour a composition from each bin 7.
As shown in FIG. 5, a lateral side of bin 7 curves outwardly so as to form spout 7b. In this way, bin 7 may be manipulated by the use of handle 7a and spout 7b so as to effectively pour its contents therefrom.
The preferred embodiments of the present invention includes a means for applying a heated wax composition to an object. Referring to FIG. 2, one such applying means preferably but not necessarily includes a plurality of trowel members 2, 3, but alternatively only one trowel member may be used.
Because heated wax compounds remain in a substantially amorphous state for only a limited period of time, each trowel member 2 and 3 preferably includes means for efficiently facilitating and enhancing the creation of the artwork within the above-mentioned time period. Such means preferably comprises trowel members 2 and 3 having a plurality of differently shaped edges, such as a substantially saw-toothed edge 2a or curved edges 3b. Further, trowel members 2 and 3 preferably but not necessarily include one or more apertures 2b. Trowel member 3 preferably includes straight edges 3a and 3c, which, when associated with each other and with curved edge 3b, form obtuse and acute angles (FIG. 2). Such trowel features allow the user to relatively quickly mold or otherwise form the heated wax so as to quickly create the desired artistic effect before the wax compound substantially solidifies. These trowel features thus allow the user to create a wider range of artistic creations which she would not otherwise be able to create.
The present invention may additionally use one or more brushes 4 together with trowel members 2 and 3 so as to provide the user with further means for applying or otherwise forming the heated wax so as to substantially quickly achieve the desired effect. Brushes 4 preferably but not necessarily include a variety of widths and/or thicknesses, such as brush 4 bristles forming a pointed end 4a, and are used to apply a melted or semi-melted wax compound to an article.
The preferred embodiments of the present invention preferably but not necessarily include an applicator for dispensing a semi-liquid composition having a decorative shape. Referring to FIG. 4, the applicator comprises flexible bag portion 5, having an opening at a first end 5a for receiving the semi-liquid composition and a second end 5b for dispensing the composition. First end 5a includes a substantially widened opening which is selectively closed by drawstring 5c in order to substantially prevent spillage. Second end 5b preferably but not necessarily includes a means for selectively attaching any of a variety of tip members 6. Each tip member 6 preferably includes an aperture defined therethrough having a different shape (FIG. 4). In this way, the composition forms a unique shape as it is dispensed from bag portion 5 through the attached cap member 6 by hand-applied pressure.
The preferred embodiments of the present invention preferably but not necessarily allow the user to create two or three dimensional artwork or decorations in wax. Two dimensional artwork is preferably but not necessarily created by heating the wax compound until it is substantially melted and applying the melted compound to a two dimensional surface using brushes 4. The two dimensional surface preferably but not necessarily comprises canvas, but in an alternative embodiment the surface comprises a substantially smooth surface such as glass, wax paper, aluminum foil, fiberglass or other resin compound.
Three dimensional artwork is preferably but not necessarily created by forming, molding or otherwise working a substantially softened wax compound into the desired shape using trowels 2, 3, and/or applicator 5, 6. Alternatively, the three dimensional artwork may be created by forming, molding or otherwise applying the heated wax over a preexisting object.
The preferred embodiments of the present invention preferably but not necessarily allow a user to create artwork temporarily in wax, thereby providing an activity in which children and adults can enjoy for hours at a time. After the wax artwork has sufficiently cooled, the wax compounds may be removed from the object to which the wax compounds were applied using trowels 2 or 3, and thereafter returned to bins 7. The removal of the wax compounds from the object is best performed by first heating trowel 2 or 3 and subsequently scraping, cutting or peeling the wax compound therefrom. In the event the artwork was created using wax compounds of different colors, the wax compounds are first sorted by color prior to returning them to the appropriate bins 7.
In use, the solid wax compounds are first placed in bins 7, and bins 7 are placed within recesses 1a of heating unit 1. If wax compounds of different colors are used to create multicolored artwork, the wax compounds for each color are placed in a separate bin 7. Thereafter, bins 7 are heated to the desired temperature by activating temperature controls 1c corresponding to bins 7 having the wax compounds therein. The selected temperature setting of temperature controls 1c depends in part upon the desired consistency of the heated wax compounds.
After the wax compounds have been sufficiently heated to the desired temperature, the heated wax compounds are removed from the bins 7 and formed or worked so as to create the desired artistic or decorative article. Trowels 2 and 3 are preferably but not necessarily used to work a substantially softened wax compound by scooping the softened wax compound onto the desired trowel and forming it into the desired shape and texture utilizing trowel edges 2a-2b and 3a-3c.
Brushes 4 are preferably but not necessarily used to apply a substantially melted wax compound to an article by brushing a layer of substantially melted wax thereon.
Bins 7 having handle 7a and spout 7b are preferably but not necessarily used to apply a heated wax compound to an article by pouring the wax compound from bin 7 onto the article.
Applicator 5 is preferably but not necessarily used to apply a semi-melted wax compound having a predetermined shape to an article. The wax compound is applied by first pouring the compound from bins 7 into bag-like member 5 via opening 5a. Thereafter, opening 5a is closed using drawstrings 5c. One of tips 6 is attached to dispensing end 5b of member 5, the selected tip member 6 having an aperture giving the desired shape of the softened wax compound as it is dispensed therethrough. The wax compound is then applied to an article by positioning tip member 6 relative to the article and selectively exerting hand pressure to bag member 5 until the wax compound is dispensed therefrom in the desired amount. Wax compounds of a different color may then be applied using the same aforementioned steps after bag member 5 and tip 6 have been cleaned or replaced.
Once the artwork has been created, the wax compounds are allowed to cool until it is substantially solidified throughout. Thereafter, the artwork may be optionally broken down so that the wax compounds may be used again. This step preferably but not necessarily comprises substantially breaking pieces of the wax compounds from the artwork and separating the pieces by color. Trowels 2 or 3 are preferably but not necessarily used to scrap or cut pieces of the wax compound from the finished artwork. Wax compound pieces are found to be more easily removed from the artwork if the working end of trowel 2 or 3 is first heated, for example by heating it with heating unit 1. Alternatively, wax compound pieces are separated from the finished artwork by another utensil or by hand.
Next, the pieces of wax compounds are returned to the appropriately bins 7. Bins 7 may be then reheated so that the wax compound pieces are melted combined with the unused wax compounds. Thereafter, the aforementioned process may be repeated so as to create another artwork in wax. Otherwise, the wax is preferably but not necessarily stored in bins 7.
The above-described apparatus and process may be used to decorate preexisting objects with wax, or to create artwork substantially entirely in wax. With regards to the latter type of creation, trowels 2, 3, pourable bins 7 and applicator 5, 6 are preferably but not necessarily used to form a three dimensional article, and thereafter trowels 2, 3 and brushes 4 are preferably but not necessarily used to add finishing touches to the surface of the article.
Although there have been described what is at present to be the preferred embodiments of the invention, it will be understood that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics thereof.
The described embodiments are, therefore, to be considered in all aspects as illustrative, and not restrictive. The scope of the invention is indicated by the appended claims, rather than by the foregoing description.
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A kit and method for making artwork in wax. The kit includes a plurality of thermally conductive containers; at least one substantially solid wax compound; a heating unit for heating each of the containers, having a separate temperature control for each container; an applicator for applying a heated wax compound to an article; and wherein each of the containers selectively slidably engages with the heating unit.
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The present invention relates to yielding fasteners, and more particularly, to a rock bolt assembly that allows controlled sag of a mine roof.
BACKGROUND OF THE INVENTION
As is well known in the mining art, in an underground mine, the roof must be supported at spaced intervals in order to assure the safety of the miners. For many years, this support was provided by shoring timbers positioned at spaced locations longitudinally along the mine tunnels. Shoring timbers have in recent years been almost totally replaced by modern rock bolt assemblies. These devices are inserted in bore holes along the rock face and serve to fasten the adjacent layers of rock together, thus preventing cave-ins. The safety of mines has improved considerably since the introduction and continued development of the modern rock bolt.
Heretofore, the rock bolt has been set in the bore hole and the rod or bolt simply tightened to a predetermined torque designed to support the strata of rock forming the rock face. The tension in the rod is usually gauged so that a safety factor is provided, i.e., the bolt assembly is tightened to a point below the elastic limit of the rod. If a serious fault develops in the rock, the tension increases and thereafter this bolt assembly imposes a safety hazard since failure may then occur at any time.
To alleviate the danger, there has been considerable development in the field of tension indicating devices, such as is shown in the U.S. Pat. No. to Cumming 3,133,468. These indicating devices help during the installation of the rock bolt assemblies, and are intended to alert mine personnel when the tension increases after installation. A spring washer or the like is flexed to varying degrees so the worker can determine when excessive tension is being approached.
These tension indicating devices are not designed for, and indeed are incapable of permitting, any more than minor rock face sagging. This is so, since the devices are merely spring devices with extremely limited travel. These prior art indicating devices also do not employ constant tension movement since mechanical springs are used. This latter feature means, that with a compression spring for example, the bolt is tensioned at a low setting equal only to some average spring force rating. When a fault occurs in the rock, the spring quickly bottoms out permitting the application of excessive force directly to the support rod. When the design force is exceeded in this way, failure inevitably occurs, just as in prior art rock bolt assemblies without indicating devices, unless the inspector is lucky enough to notice the change and has replaced the bolt before another rock shift occurs.
From this background, I have recognized a need for providing a rock bolt that allows reasonable rock sag in a mine and does so while maintaining a constant tension in the rod or bolt. The constant tension feature would be self-adjusting and thus prevent the elastic limit of the bolt from ever being reached. Extended travel is also necessary so that a rock fault within proven limits for a particular area may be accommodated. My theory is that if shifting of rock can occur while still maintaining the rock face in tact supported by the design tension, then cave-ins due to rock shifting can be virtually eliminated. This, in turn, will result in saving of lives, and it will also represent a considerable increase in efficiency since closing of mine shafts and clean up from wall failures will be minimized.
OBJECTIVES OF THE INVENTION
With the foregoing considerations in mind, it is a main object of the present invention to provide a rock bolt assembly that allows controlled yielding of the rock wall.
It is another object of the present invention to provide a rock bolt assembly that utilizes a simple design with the addition only of a special collar that allows controlled, constant tension movement of the wall.
It is still another object of the present invention to provide a yielding rock bolt assembly wherein the coupling means that provides the yield is characterized by deformation of threads by die on a sliding collar.
BRIEF DESCRIPTION OF THE INVENTION
A yielding rock bolt assembly includes a rod extending between the two areas to be fastened together, anchor means at one end, i.e., at the inner end of the bore, a collar movable along the rod and deformable holding means on the rod interacting with the collar. The deformable holding means and the collar couple the rock face support plate at the outer end of the bore and the expandable anchor at the inner end, thus holding the adjacent strata of rock together. As will be clear to those skilled in the art, the yieldable coupling concept of the present invention can be utilized in other areas where a controlled, constant tension movement between two areas is desirable. A coupling for parts of high pressure vessels to allow controlled expansion or any other application for a "mechanical fuse" is within the purview of the broader aspects of my invention.
The deformable holding means on the rod is preferably rolled threads having alternate crests and valleys. The collar includes a female die member adapted to mate with the threaded portion of the rod with an interference fit. The rod is tensioned during installation to a point where the upper few threads are extruded and flattened. The crest of the first few threads are actually moved by cold flow into the valleys between. This extruding action provides a frictional holding interface allowing controlled movement of the collar down the threaded section. That is, when this threshold tension used to initially set the coupling is exceeded, additional movement is allowed due to a developing fault thereby preventing the application of excessive force as would have occurred with the use of prior art rock bolt assemblies. Thus, the wall face is allowed to move inward from its original position to a new position where the same holding force and tension in the bolt is re-established.
As an incidental feature, when a fault has developed, the inspector in the mine can easily read the position of the coupling to see the extent of movement and can then take extra precautions to re-establish the shoring of the rock wall if necessary. If only a relatively small area has been traversed by the sagging of the rock, then the bolt assembly can by choice be left in position since upon the occurrence of another fault, the collar merely moves down an additional distance over the extended thread portion.
The die of the collar has a tapered leading bore portion and a straight bore portion, both of which are hardened to prevent wear. The leading portion allows the threads to be gradually crushed during the initial deformation adding smoothness and assuring controlled cold flow of the material, as desired. With the interference fit between the threads and the die, and more specifically a force fit between the straight portion and the collapsed threads, the necessary frictional interface is provided assuring a constant tension on the rod. The threads in the tapered portion act as a wedge providing the frictional holding force.
Since the holding action is a straight extruding action, the forces acting on the rod of the bolt assembly are pure tension. The spiral formation of the threads does not add any perceptable torque load to the bolt or rod. Thus, the strain on the bolt and the chances of failure by fatigue are further minimized.
To initially set the expandable anchor at the inner end of the bore, a cap nut may be placed on the bottom of the threaded rod. The cap nut holds the collar up clear of the supporting plate during this operation. A socket engaging the cap nut and driven by a suitable torque limiting power tool, positions the anchor and turns the rod until the anchor is set. Reversing the tool removes the cap nut and the plate supporting nut is then placed on the collar and properly torqued to establish the desired rock face support.
Still other objects and advantages of the present invention will become readily apparent to those skilled in this art from the following detailed description, wherein I have shown and described only the preferred embodiment of the invention, simply by way of illustration of the best mode contemplated by me of carrying out my invention. As will be realized, the invention is capable of other and different embodiments, and its several details are capable of modification in various obvious respects, all without departing from the invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a detailed view partially in cross-section showing the fastener assembly mounted within a bore in a rock environment;
FIG. 2 is a detailed view of the yieldable coupling means of the assembly after a rock fault has developed; and
FIG. 3 is a detailed view of the lower portion of the assembly illustrating one method of torquing the rock bolt to set the anchor.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference to the structure shown in FIG. 1 representing the preferred embodiment of the invention, a more detailed description and analysis of the principles of the invention can be undertaken. A rock bolt assembly 10 is mounted in a rock formation R within a drilled bore B. At the upper part of FIG. 1 is illustrated the inner end E 1 of the bore B formed in a first area or strata of rock to be coupled to the lower end E 2 adjacent wall face W.
A standard expandable anchor 11 is locked in the expanded mode grasping the walls of the bore end E 1 . In the center of the assembly is rod or shank portion of the bolt 13 (part broken away in drawing to conserve space). At the lower or outer end of the assembly 10 is a yieldable coupling device 14 constructed in accordance with the principles of the present invention. It will be clear that the rock bolt shown and described is a species of a generic fastener assembly that can be utilized in many environments where controlled, constant tension relative movement between two areas is desired, as will be more fully appreciated in the description below.
In the FIG. 1 showing, it will be understood that the anchor 11 has already been set. This is accomplished by torquing the bolt of the assembly prior to fully assembling the coupling means, as will be described later.
The yieldable coupling device 14 includes a collar, generally designated by the reference numeral 20. The collar 20 includes an upper tubular die section 21 with a tapered leading entrance portion 22 and a straight die portion 23. This entire die section has a sliding fit on the rod 13 so that the entire collar may move up and down as desired, prior to the collar 20 being set into holding position as shown.
The lower part of the collar 20 comprises an extension section 25 that surrounds threads or threaded section 26 formed on the rod 13. These threads form the deformable holding means that cooperates with the die 21 at the top of the collar. At the lower or outer end of the collar 20, a plate 27 is received with a threaded nut 28 engaging external threads 29 on the collar 20 to provide the support to the face W.
In order to illustrate the principles of the present invention, a fault line F has been shown across the rock structure R. This can be an interface between two different rock strata or a crack in any particular one of these layers. This is a typical situation and is intended merely to illustrate the principles involved in a yielding bolt when the fault develops, as will be seen more in detail later in the discussion of FIG. 2.
The basic installation and operation of the coupling device 14 is very simple. After the anchor 11 has been set and the collar 20 is positioned with the die 21 resting by gravity against the first thread (see dotted line outline of die 21 in FIG. 1), the plate 27 is simply slipped over the threaded end 29 of the collar 20. The nut 28 is next put on to draw the die 21 snugly against the first thread of the threads or threaded section 26. With a torque wrench, or with other suitable wrench and tension measuring means, the nut 28 is tightened, drawing the die 21 downwardly over the first group of threads 26a (note full line position of FIG. 1). The threads as they are forced into the entrance portion 22 of the die 21 are progressively deformed or crushed with the crests of the threads cold-flowing into the alternate valleys (see crushed threaded section 26a). As the first threads 26a substantially fill the straight die portion 23, a desired holding tension in the rod 13 is reached and the load is supported.
The entire internal length of the die 21, including the entrance portion 22 and the straight die portion 23 has an interference fit causing the deformation of the threads 26a. The surface engagement between the die 21 and the crushed threads 26a establishes a frictional holding interface to provide the desired tension in the bolt assembly.
When tensioning the bolt assembly 10, an initial threshold level is selected that is clearly within the elastic limit of the rod 13. This lower limit and the fact that there is substantially no torque forces involved, maintains the rod 13 at a tension where fatigue is minimized. The rock is held under normal conditions, and then under emergency conditions caused by separation of rock, as shown by developed fault F 1 in FIG. 2, there is an increase in tension and a resultant yielding of coupling 14 to allow the rock to sag. The relative sliding movement in the coupling 14 prevents any significant increased tension and consequently, of course, maintains that tension well within the safety limits of the rod or bolt 13.
To explain further, FIG. 2 shows the fault F having developed into the fault F 1 within the rock R and the movement that has occurred in the coupling 14. The straight die portion 23 has moved into engagement with the upper deformed threads 26a and additional threads 26b are now initially deformed by a wedge effect in the entrance portion 22. Once a thread has been fully deformed by crushing the threads in the straight die portion 23, the frictional holding interface is not significantly increased, and the design tension is thus substantially maintained and is fully effective to check further rock separation.
It will be noticed with the development of the fault F 1 , the distal end of the threaded portion 26 has receded into the collar 25. This gives the inspector in the mine ready recognition that this area of the mine ceiling has experienced some rock sag. By checking the distance the end has moved up into the collar, the extent of the rock fault F 1 can be readily determined.
Most importantly, however, unlike in the prior art, with the rock fault F 1 having occurred, there is no eminent danger of failure of the bolt. The extended portion of threads 26 within the collar 20 is still available for enlargement of the fault F 1 or accommodation of other faults as they occur. And, it is clear that regardless of the size of the fault (within the gauged limits of the threaded portion 26), the rod 13 is maintained under substantially constant design tension. The additional movement of the collar 20 down the threaded portion 26 occurs only as is necessary to accommodate the forces within the rock R. The rock is held by the bolt without slackening of the tension that could cause other rock shifting in the immediate area.
A salient feature of the rock bolt assembly 10 of the present invention is that it is simple and reliable in construction. It makes use of standard rock bolt components and the collar 20 is relatively inexpensive to produce. The tolerances required for the interference fit between the die 21 and the cooperating threads 26 are not critical. Also, only the internal face of the die portions 22, 23 need be hardened. This prevents stripping or wearing of the metal in the collar as the threads 26 are engaged, thus assuring maintenance of the substantially constant tension regardless of how far down the threads the die has moved.
During the actual manufacture of the inventive bolt assembly 10, the collar 20 is required to be first inserted on the standard bolt 13 and moved toward the anchor 11 as far as possible. The lower end of the collar at this point clears the rod 13 where the threads 26 are to be formed. The threads 26 are formed by a cold-rolling operation. The material forming the crest of the threads is moved radially outwardly to a diameter greater than the diameter of the rod 13 thus providing requisite interference relationship.
As shown in FIG. 1, the crests are substantially the same diameter as the mouth of the tapered entrance portion 22. The crests extend above the nominal diameter of the rod 13 and the valleys are below. As the collar 20 is drawn downwardly to tension the rod 13, the initial threads 26a are crushed by cold-forming with a smooth, controlled action. From the point where the upper threads 26a begin to enter the entrance portion 22, there is an increase in tension up to the maximum design tension. After the first group of threads has fully entered the die portion 23, no further wedging action takes place, and thus from this point on it is substantially a constant tension operation, as explained above.
The expandable anchor 11 can be initially set by simply torquing the rod 13 before the yieldable coupling 14 is assembled, as previously pointed out. This can be done in any conventional way, but normally care should be taken not to prematurely strip or otherwise deform the threads 26. This is important so that in the event that the lower end of the threaded portion 26 is reached by the die during a support operation due to the development of an abnormally large fault F 1 , the tension will remain the same and the bolt assembly 10 will thus hold with the design tension being maintained. Thus, one way of activating the anchor 11 would be to install a cap nut on the end of the threaded portion 26 and then draw the nut down tight or until it bottoms out against the distal end of the rod 13. As shown in FIG. 3, the collar 20 is conveniently temporarily moved upwardly to clear the lower section of the threaded portion 26. By using the plate 27, and holding the nut 30 upwardly during the tightening operation, such as by use of a socket and power tool urged upwardly from below, the anchor 11 is set at exactly the desired position. With each bolt assembly 10 uniformly set, the incidental indication function of the distal end of the rod 13 is operative. When the anchor 11 is fully expanded, the cap nut 30 is simply backed off, the collar 20 drops down into position, and the threaded support nut 28 is attached to the threads 29 on the collar to activate and set the coupling device 14.
In review, a yielding rock bolt 10 has been provided offering new potential for safety and efficiency in the mines. When a fault F develops in the supported rock, a controlled, substantially constant tension yielding of the coupling device 14 occurs. This provides exactly the right amount of relief needed to accommodate the fault F and allow the rock wall W to sag. The rock R is maintained steady under the substantially constant tension support thereby minimizing the chances of further loosening of the rock. However, in the event of additional rock separation, the collar 20 of the coupling device 14 simply moves further down the extended threaded portion 26 and stops just at the right position to again maintain the constant tension support. In effect, and simply put, the rock face W is allowed to move inward from its original position due to a developing fault to a new position where the design holding force is automatically re-established. The rock bolt assembly 10 is easy and inexpensive to fabricate, has a simple built-in indicating feature and is easy to install.
In this disclosure, there is shown and described only the preferred embodiment of the invention, but, as aforementioned, it is to be understood that the invention is capable of use in various other combinations and environment and is capable of changes or modifications within the scope of the inventive concept as expressed herein.
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A bolt assembly for supporting a mine roof or the like is disclosed having a yieldable coupling means at least at one end to allow controlled sagging of the rock to prevent exceeding the elastic limit of the bolt. An expandable anchor may be provided at the other end. The coupling means includes a collar having a die movable along deformable threads of the bolt when the rock load increases. This relative movement provides relief thereby assuring against the bolt becoming excessively tensioned. The die deforms the threads by coldflow extruding and flattening action against the crest of the threads. This action forms a frictional holding interface between the bolt and the collar and maintains substantially constant tension in the bolt. A nut on the collar transmits the supporting force to the rock face. A removable cap nut may be threaded onto the bolt to properly pre-position the parts and transmit torque to the anchor during installation.
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CROSS REFERENCE TO RELATED APPLICATION
This application is a divisional of U.S. Ser. No. 10/834,974, filed on Apr. 30, 2004 now U.S. Pat. No. 7,231,926. This application, in its entirety, is incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a mascara brush, and more particularly, to a mascara brush, wherein an application portion as a means for applying a mascara liquid to eyelashes and a comb for arranging the eyelashes are simultaneously formed on a single brush rod so that the application of the mascara liquid to the eyelashes and the arrangement of the eyelashes can be performed at one time.
2. Description of the Prior Art
Mascara is one of cosmetics used by women to apply mascara liquids of various colors to their eyelashes so that their eyes can look better in an esthetic sense. Generally, as shown in FIG. 18 , a mascara brush 100 comprises a container 150 for containing a mascara liquid, a grip 160 for opening and closing the container 150 , a brush rod 120 extending downwardly from the grip 160 , and a brush part 130 formed at the brush rod 120 . The mascara liquid is used in such a manner that the brush part 130 is smeared with the mascara liquid through engagement or disengagement of the grip 160 to or from the container 150 .
Particularly, depending on the length and configuration of the bristles, the mascara brush 100 constructed as above is manufactured to be adapted to various functions such as volume-up (effect of allowing eyelashes to be seen abundantly), curling (effect of upwardly curling distal ends of eyelashes), long lash (effect of allowing eyelashes to appear longer) and clean (effect of preventing eyelashes from being entangled) for eyelashes.
As shown in FIG. 18 , the conventional mascara brush that has been typically used is manufactured in such a manner that bristles 131 of the brush part 130 with a generally constant length are disposed between two stands of wires and the wires are then twisted several times so that the brush part 130 can have a cross section in the form of any of various shapes including circular, triangular and sectorial shape about a wire shaft 121 . The effects of volume-up, curling, long lash and clean can be obtained with respect to the respective shapes of the cross section of the brush part 130 .
The basic function of the mascara brush is to evenly apply a viscous mascara liquid to eyelashes and to appropriately comb the eyelashes by means of the brush part so that the eyelashes are not entangled. Since the bristles 131 extend radially along a helical path due to the twisting of the wires in the conventional mascara brush 100 , a great deal of mascara liquid can be accommodated between the respective bristles 131 . Thus, the conventional mascara brush can make the eyelashes appear voluminous. However, eyelashes often become entangled due to the viscosity of the mascara liquid. Accordingly, there is inconvenience in that the eyelashes should be arranged using an additional arranging instrument, or make-up application should be performed again after the excess mascara liquid is removed.
A mascara brush 200 for solving the entanglement phenomenon of eyelashes of the previous mascara brush, as shown in FIG. 19 , comprises a brush rod 220 of which a lower end has a diameter smaller than that of an upper end thereof, and a brush part 230 that is formed at a side surface of the lower end of the brush rod and has bristles 231 formed by a separate manufacturing apparatus from the same synthetic resin material as the brush rod 220 and then fixed to the brush rod 220 . The bristles 231 are arranged longitudinally in a line on the side surface of the lower end of the brush rod 220 to take the shape of a linear comb. Thus, when a mascara liquid is applied to eyelashes, it is applied to the eyelashes while permeating through the eyelashes due to the combing of the linear brush part 230 . Accordingly, the effects of clean and long lash can be obtained.
Meanwhile, the bristles 231 of the mascara brush 200 are formed of a material similar to a material for the brush rod 220 , which is a synthetic resin such as polyamide. The bristles 231 are completed by slitting a mass of the synthetic resin constructing the brush part 230 into fine strands. In view of properties of the synthetic resin, however, the bristles 231 cannot be formed finely to such as extent as the bristles 131 of the conventional mascara brush 100 shown in FIG. 16 . Further, since the wide spacing of the respective bristles 231 deteriorates their capability to accommodate a mascara liquid, it is difficult to apply the mascara liquid in case of tufty or long eyelashes. Moreover, although the linearly arranged bristles 231 applies the mascara liquid to eyelashes in such a manner that they comb the eyelashes upon application of the mascara liquid, thereby preventing the entanglement phenomenon of the eyelashes, there is a problem in that the effects of volume-up and curling of the eyelashes are deteriorated.
SUMMARY OF THE INVENTION
The present invention is conceived to solve the aforementioned problems in the prior art. Accordingly, an object of the present invention is to provide a mascara brush, wherein a single brush rod of the mascara brush is formed with both an application brush part with an application portion for applying a mascara liquid to eyelashes and an arrangement brush part with a comb for arranging the eyelashes in order to simultaneously perform the application of the mascara liquid and arrangement of the eyelashes, thereby conveniently imparting the effects of clean, long lash and curling to the eyelashes through a single process, the structure of the mascara brush is simplified so that a manufacturing process can be relatively simplified, and stability in use can be obtained due to the securely coupled state.
According to the present invention for achieving the object, there is provided a mascara brush, comprising an application brush part with an application portion formed on an outer circumferential surface of a rod thereof to apply a mascara liquid to eyelashes; and an arrangement brush part including a fixing stand coupled to the application brush part, and a comb formed on an outer peripheral surface of the fixing stand. The application brush part is formed with a cutaway portion by longitudinally cutting away a section of the application portion, and the comb is placed in the cutaway portion so that the arrangement brush part can be integrated with the application brush part.
The rod of the application brush part may be constructed by twisting parts of a metal wire, and the application portion may be fixedly formed by interposing a plurality of bristles between the parts of the metal wire and twisting the parts of the metal wire.
The rod of the application brush part may be injection molded from a synthetic resin such that the application portion is formed on the outer circumferential surface of the rod.
The fixing stand may be sized to correspond to the cutaway portion of the application brush part, an upper end of the fixing stand may be formed with a fitting hole into which the rod is fixedly inserted and a lower end of the fixing stand may be formed with a fitting recess into which a distal end of the rod on the side of the application portion is fixedly inserted, and the comb may be formed on a side surface of the fixing stand in a longitudinal direction of the fixing stand.
The fixing stand may be formed to take the shape of a cylinder and formed with a central insertion bore longitudinally therethrough so that the rod can be inserted into the insertion bore, a lower end of the fixing stand may be formed with a fitting recess into which a distal end of the rod on the side of the application portion is fixedly inserted, both sides of the fixing stand may be perforated to have open windows such that existing sections of the application portion of the application brush part protrude outwardly through the windows, and the comb may be formed on a side surface of the fixing stand in a longitudinal direction of the fixing stand.
A section of the application portion fixed at the distal end of the rod on the side of the application portion may be removed and a ring may be formed to be exposed at the distal end of the rod.
A distal end of the rod with the application portion injection molded thereon may be performed to form a ring.
The arrangement brush part coupled to the application brush part may comprise the fixing stand for fixing and supporting the application brush part, and the comb formed on a side surface of the fixing stand, the fixing stand may be sized to correspond to the cutaway portion of the application brush part, an upper end of the fixing stand may be formed with a fitting hole into which the rod is fixedly inserted, and a lower end of the side surface may be formed with a protruding, coupling piece adapted to be fixedly inserted into the ring of the rod.
The arrangement brush part coupled to the application brush part may comprise the fixing stand for fixing and supporting the application brush part, and the comb formed on a side surface of the fixing stand, the fixing stand may be formed to take the shape of a tube and formed with a central insertion bore longitudinally therethrough so that the rod of the application brush part can be inserted into the insertion bore, both sides of the fixing stand may be perforated to have open windows such that existing sections of the application portion of the application brush part protrude outwardly through the windows, and a lower end of the side surface may be formed with a protruding, coupling piece adapted to be fixedly inserted into the ring of the rod.
The cutaway portion may be formed in an angular range of 30 to 120 degrees about the center of the cross section of the application brush part.
The cutaway portions may be formed by cutting away lateral side sections of the application portion that are symmetric with each other with respect to the cross section of the application brush part.
One or more columns of combs may be formed on the arrangement brush part in a longitudinal direction of the fixing stand.
A plurality of columns of combs are formed on the fixing stand in a zigzag manner.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and advantages of the present invention will become apparent from the following description of preferred embodiments given in conjunction with the accompanying drawings, in which:
FIG. 1 is a front view of a mascara brush according to a first embodiment of the present invention;
FIG. 2 is a front view showing a state where an application brush part and an arrangement brush part of the mascara brush shown in FIG. 1 are separated from each other;
FIG. 3 is a bottom view of the application brush part of FIG. 2 ;
FIG. 4 is a perspective view showing that a plurality of columns of combs are formed at the arrangement brush part of FIG. 2 ;
FIG. 5 is a bottom view showing a state where the application brush part of FIG. 2 and an arrangement brush part with a column of comb are coupled to a brush rod of the mascara brush;
FIG. 6 is a bottom view showing a state where the application brush part of FIG. 2 and an arrangement brush part with a plurality of columns of combs are coupled to a brush rod of the mascara brush;
FIGS. 7 a and 7 b are front and bottom views of an application brush part according to a second embodiment of the present invention, respectively, wherein cutaway portions are formed symmetrically;
FIGS. 8 a and 8 b are front and bottom views of an arrangement brush part according to the second embodiment of the present invention, respectively, wherein a fixing stand having a configuration corresponding to that of the application brush part with the cutaway portions formed symmetrically is provided;
FIGS. 9 a and 9 b are front and bottom views showing a state where the application brush part of FIG. 7 a and the arrangement brush part of FIG. 8 a are coupled to each other, respectively;
FIGS. 10 a, 10 b and 10 c are a front view, a side view and a sectional view through line A-A, respectively, showing an application brush part according to a third embodiment of the present invention;
FIGS. 11 a and 11 b are a front view and a sectional view through line B-B, respectively, showing an arrangement brush part according to the third embodiment of the present invention;
FIGS. 12 a and 12 b are a front view and a sectional view through line C-C, respectively, showing a state where the application brush part and the arrangement brush part according to the third embodiment of the present invention are coupled to each other;
FIGS. 13 a and 13 b are a front view and a sectional view through line A′-A′, respectively, showing an application brush part according to a fourth embodiment of the present invention;
FIGS. 14 a and 14 b are a front view and a sectional view through line B′-B′, respectively, showing an arrangement brush part according to the fourth embodiment of the present invention;
FIGS. 15 a and 15 b are a front view and a sectional view through line C′-C′, respectively, showing a state where the application brush part and the arrangement brush part according to the fourth embodiment of the present invention are coupled to each other;
FIGS. 16 a, and 16 b and 16 c are a front view and bottom views showing application brush parts according to further embodiments of the present invention;
FIGS. 17 a, and 17 b and 17 c are a front view and bottom views showing that a ring portion is formed at a lower end of a rod of the application brush part of FIG. 16 a; and
FIGS. 18 and 19 are perspective views of conventional mascara brushes.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, preferred embodiments of a mascara brush of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is a view showing a mascara brush according to a first embodiment of the present invention in a disengaged state. The mascara brush 1 comprises a container 5 for containing a mascara liquid, a grip 6 for opening and closing the container 5 , a brush rod 2 extending downwardly from the grip 6 , and an application brush part 3 and an arrangement brush part 4 formed at a lower end of the brush rod 2 .
The brush rod 2 fixed to the grip 6 is in the form of a rod which has a predetermined length such that it can be inserted into the container 5 and the application brush part 3 can be then smeared with the mascara liquid, and has a diameter smaller than that of a mouth of the container 5 such that it can pass through the mouth of the container 5 . At the lower end of the brush rod 2 , a rod 21 with the application brush part 3 fixed thereto is coupled to a fixing stand 40 formed with the arrangement brush part 4 .
FIG. 2 is a front view showing a state where the application brush part and the arrangement brush part are separated from each other.
The application brush part 3 is a means for receiving the mascara liquid and applying it to eyelashes. The application brush part 3 is constructed by interposing a plurality of bristles having a constant length between and perpendicularly to two parts of a metal wire folded at the center thereof and spirally twisting the two wire parts several times. Thus, the bristles are fixed radially to the rod 21 formed through the twisting of the wire parts, thereby forming an application portion 7 .
Further, as shown in FIG. 3 , a side surface of the application brush part 3 is formed longitudinally (perpendicularly to the cross section of the application brush part 3 ) with a cutaway portion 31 by cutting away a section of the application portion 7 that is fixed to the wire shaft constructing the rod 21 . At this time, the cutaway portion 32 is formed by longitudinally cutting away a section of the application portion 7 within an angular range of about 30 to 120 degrees about the center of the cross section of the application brush part 3 .
Then, the application brush part 3 constructed as above is fixedly coupled to the lower end of the brush rod 2 to be integrated with the brush rod 2 .
The arrangement brush part 4 shown in FIG. 2 is a means for arranging the eyelashes smeared with the mascara liquid by the application brush part 3 , and has a comb 8 protruding from an outer surface of the fixing stand 40 .
The fixing stand 40 is to fix the comb 8 to the cutaway portion 31 of the application brush part 3 . The longitudinal length of the fixing stand 40 is identical with or slightly larger than that of the rod 21 extending the lower end of the brush rod 2 . Upper and lower ends of the fixing stand 40 are formed with upper and lower flanges that extend in a direction perpendicular to a side surface 41 corresponding to the longitudinal length of the fixing stand 40 and have a diameter identical with that of the brush rod 2 .
The upper flange of the fixing stand 40 is formed with a fitting hole 42 through which the rod 21 is inserted so that the fixing stand 40 is integrated with the application brush part 3 . The lower flange of the fixing stand 40 is formed with a fitting recess 43 into which a distal end of the rod 21 on the side of the application portion 7 is fixedly inserted when the rod 21 inserted into the fitting hole 42 is lowered. Further, since the comb 8 formed on the side surface 41 of the fixing stand 40 is placed in the cutaway portion 31 formed in the application portion 7 of the application brush part 3 , the cross section of the side surface of the fixing stand 40 takes the shape of a sector with a central angle of about 30 to 120 degrees corresponding to the shape of the cutaway portion 31 . The fixing stand 40 is in the form of “ ” as a whole.
The comb 8 has one or more teeth thereof protruding vertically from the side surface 41 of the fixing stand 40 in order to comb the eyelashes. The teeth of the comb 8 are formed in a line to protrude vertically from the side surface of the fixing stand 45 over a length similar to that of the application portion 7 fixed to the rod 21 of the application brush part 3 . Here, the teeth of the comb 8 are injection molded using a precision mold from the same material as the fixing stand 40 , i.e. natural resin, synthetic resin including polyamide, or the like, so that they can be formed to be thicker and more robust than the application portion 7 of the application brush part 3 . The respective teeth of the comb 8 are formed in a line at an interval of about 0.1 to 1 mm. Accordingly, the arrangement brush part 4 takes the shape of a linear comb.
As for the comb 8 of the arrangement brush part 4 , it is preferred that one or more columns of combs 8 be formed perpendicularly to the side surface 41 of the fixing stand 40 , as shown in FIG. 4 . Moreover, teeth of a column of comb 8 and teeth of the next column of comb may be formed to be in the same horizontal planes or to be staggered in a zigzag manner.
To fix the arrangement brush part 4 constructed as above to the application brush part 3 , the fitting hole 42 of the fixing stand 40 is fitted around the rod 21 , the fixing stand 40 is then adjusted in its position such that the side surface 41 of the fixing stand 40 is placed in the cutaway 32 of the application brush part 3 , and the fitting recess 43 of the fixing stand 40 is fitted around the distal end of the rod 21 on the side of the application portion 7 . Consequently, the fixing stand 40 and the rod 21 are coupled to each other.
Here, since the application portion 7 does not extend up to the distal end of the rod 21 , the distal end of the rod 21 is press-fitted into the fitting recess 43 and the rod 21 is then fixedly coupled to the fixing stand 40 by means of various methods including adhesive bonding, thermal bonding and the like.
As described above, both the application brush part 3 and the arrangement brush part 4 are coupled to the single brush rod 2 . Thus, the application brush part 3 is formed at a side of the brush rod 2 and the arrangement brush part 4 is formed at the other side of the brush rod 2 so that the mascara brush 1 can have an actiniform configuration as a whole.
Further, lower portions of the application and arrangement brush parts 3 and 4 of the mascara brush 1 are cut slantingly toward their distal ends to more easily facilitate access to short eyelashes located at either side of the eyelid.
Therefore, when the mascara brush 1 constructed as above is smeared with the mascara liquid and then used, the application brush part 3 with the application portion 7 receives a large amount of mascara liquid. Thus, when the mascara liquid is applied to the eyelashes by the application brush part 3 formed at a side of the mascara brush 1 , the application portion 7 of the application brush part 3 comes into contact with the eyelashes and applies the mascara liquid to the eyelashes, thereby imparting volume-up effect to the eyelashes. Then, the eyelashes are arranged using the arrangement brush part 4 formed in the form of a comb at the other side of the mascara brush 1 . The teeth of the comb 8 deeply penetrate between the respective eyelashes to prevent entanglement of the eyelashes and simultaneously support the eyelashes throughout the use of the arrangement brush part. Therefore, the effects of volume-up, long lash, curling and clean are exhibited.
At this time, since the linear comb 8 formed at the arrangement brush part 4 is also smeared with the mascara liquid, the effects of long lash, curling and clean can be imparted to the eyelashes even when the mascara liquid is applied to the eyelashes using only the arrangement brush part 4 .
Moreover, when the mascara brush 1 having the arrangement brush part 4 with the plurality of columns of combs 8 is used, the plurality of staggered columns of combs 8 more easily penetrate between the eyelashes to apply the mascara liquid to the eyelashes. Therefore, even when only the arrangement brush part 4 formed with the plurality of columns of combs 8 is used, the effects of volume-up, long lash, curling and clean can be imparted to the eyelashes.
FIGS. 7 a and 8 a show a second embodiment of the present invention.
An application brush part 3 of the second embodiment is constructed by interposing a plurality of bristles having a constant length between and perpendicularly to two parts of a wire folded at the center thereof and spirally twisting the two wire parts a certain number of times, as described above. Thus, an application portion 7 thus formed is fixed to the rod 21 formed through the twisting of the wire parts.
As shown in FIGS. 7 a and 7 b, the application brush part 3 is provided with cutaway portions 32 formed by longitudinally cutting away some sections of the application portion 7 fixed to the rod 21 symmetrically with respect to the cross section of the application brush part 3 . Thus, the application portion 7 of the application brush part 3 has a symmetric configuration.
That is, in view of the four directions in the cross section of the application brush part 3 , north and south sections of the application portion 7 of the application brush part 3 are cut away in a symmetric manner to form the cutaway portions 32 . Thus, only east and west sections of the application portion 7 except the cutaway portions 32 symmetrically remain in the application brush part 3 .
As shown in FIGS. 8 a and 8 b, an arrangement brush part 4 that serves as a means for arranging eyelashes smeared with the mascara liquid when coupled to the application brush part 3 has combs 8 protruding outwardly from a side surface 51 of a fixing stand 50 .
The fixing stand 50 takes the shape of a cylinder and is formed with a central insertion bore 52 longitudinally therethrough so that the rod 21 of the application brush part 3 can be inserted into the insertion bore 52 to cause the fixing stand to be coupled to the application brush part 3 . In order to fix the rod 21 , a lower end of the fixing stand 50 is formed with an insertion recess 53 into which the distal end of the rod 21 on the side of the application portion 7 is fixedly inserted. Further, the side surface 51 of the fixing stand 50 is perforated symmetrically to have open windows 54 with a predetermined size such that when the fixing stand is coupled to the application brush part 3 with the cutaway portions 32 symmetrically formed therein, the existing sections of the application portion 7 of the application brush part 3 protrude outwardly through these windows.
That is, in view of the four directions in the cross section of the fixing stand 50 , the open windows 54 of the fixing stand 50 are formed symmetrically to correspond to the east and west sections of the application portion 7 of the application brush part 3 , and the combs 8 are formed symmetrically on north and south regions of the side surface 51 of the fixing stand 50 .
Therefore, in order to couple the arrangement brush part 4 to the application brush part 3 , the insertion bore 52 of the fixing stand 50 is fitted around the rod 21 with the application portion 7 formed thereon, and at the same time, the cutaway portions 32 of the application brush part 3 are placed at closed regions of the side surface 51 of the fixing stand 50 while the existing sections of the application portion 7 of the application brush part 3 are placed in the open windows 54 of the fixing stand 50 . Then, the distal end of the rod 21 on the side of the application portion 7 is inserted into the insertion recess 53 of the fixing stand 50 to couple the fixing stand 50 and the rod 21 to each other.
Accordingly, both the application brush part 3 and the arrangement brush part 4 are provided on the single brush rod 2 . As shown in FIGS. 9 a and 9 b, the existing sections of the application portion 7 of the application brush part 3 are placed symmetrically in the east and west directions of the brush rod 2 , and the combs 8 of the arrangement brush part 4 are placed symmetrically in the north and south directions of the brush rod 2 . When the mascara brush 1 with the integrally formed application and arrangement brush parts 3 and 4 is used for applying the mascara liquid to the eyelashes, the effects of volume-up, long lash, curling and clean can be imparted to the eyelashes.
FIGS. 10 a and 11 a are front views showing an application brush part 3 and an arrangement brush part according to a third embodiment of the present invention in a decoupled state, respectively. Although the brush parts of this embodiment are substantially identical with those shown in FIG. 2 in view of their configurations, the configurations of lower ends thereof are different from each other.
FIG. 10 a is a front view of the application brush part, FIG. 10 b is a side view of FIG. 10 a, and FIG. 10 c is a sectional view taken along line A-A of FIG. 10 a.
The application brush part 3 is constructed by interposing a plurality of bristles between two parts of a wire folded at the center thereof and spirally twisting the two wire parts several times. Thus, an application portion 7 consisting of the bristles is fixed to the rod 21 formed through the twisting of the wire parts. Further, the application brush part 3 is formed longitudinally with a cutaway portion 31 by cutting away a section of the application portion 7 within an angular range of 30 to 120 degrees in the cross section of the application brush part 3 .
A section of the application portion 7 fixed to a lowest end of the rod 21 through the twisting of the wire parts is removed so that a ring 22 can be exposed at the lowest end of the rod 21 . With the ring 22 , the application brush part 4 to be described later is coupled to the application brush part 3 .
FIG. 11 a is a front view of the application brush part, and FIG. 11 b is a sectional view taken along line B-B of FIG. 11 a.
The arrangement brush part 4 comprises a “ -shaped ” fixing stand 80 , and a comb 8 formed on a side surface 81 of the fixing stand 80 .
The side surface 81 defining the longitudinal length of the fixing stand 80 has a length identical with or slightly shorter than that of the rod 21 . An upper flange extending from the side surface 81 in a direction perpendicular thereto is formed with a fitting hole 82 into which the rod 21 of the application brush part 3 is inserted. Particularly, a lower flange extending from the side surface 81 in a direction perpendicular thereto is formed with a protruding, coupling piece 85 that is to be fixedly inserted into the ring 22 of the rod 21 . Here, since the upper flange of the fixing stand 80 comes into contact with the lower end of the brush rod 2 , it has a diameter identical with that of the brush rod 2 . Further, since the coupling piece 85 of the fixing stand 80 should be inserted into the ring 22 formed at the rod 21 , it has a proper diameter corresponding to the inner diameter of the ring 22 .
Moreover, since the side surface 81 of the fixing stand 80 on which the comb 8 is formed should be placed in the cutaway portion 31 of the application brush part 3 , it has a cross section conforming to the cross section of the cutaway portion 31 in view of their shapes.
Therefore, in order to fix the arrangement brush part constructed as above to the application brush part as shown in FIGS. 12 a and 12 b, the fitting hole 82 of the fixing stand 80 is first fitted around the rod 21 with the application portion 7 and the side surface 81 of the fixing stand 80 is adjusted in its position to be in contact with the cutaway portion 31 of the application brush part 3 . When the rod 21 is lowered up to the lower flange of the fixing stand 80 , the coupling piece 85 of the fixing stand 80 is inserted into the ring 22 of the rod 21 . Thus, the application brush part 3 and the arrangement brush part 4 are coupled to each other. At this time, in order to ensure more secure coupling of the coupling piece 85 to the ring 22 of the rod 21 , a tip of the coupling piece 85 inserted into the ring 22 is bent or subjected to thermal bonding. As a result, the coupled state of the ring 22 and the coupling piece 85 can be firmly maintained.
FIGS. 13 a and 14 a show an application brush part and an arrangement brush part according to a fourth embodiment of the present invention, respectively. Although the brush parts of this embodiment are substantially identical with the application and arrangement brush parts 3 and 4 shown in FIGS. 7 a and 8 a in view of their configurations, the configurations of lower ends thereof are different from each other.
FIG. 13 a is a front view of the application brush part, and FIG. 13 b is a sectional view taken along line A′-A′ of FIG. 13 a.
The application brush part 3 of the fourth embodiment is constructed by interposing a plurality of bristles between two parts of a wire folded at the center thereof and spirally twisting the two wire parts a certain number of times. Thus, the application portion 7 thus formed is fixed to the rod 21 formed through the twisting of the wire parts. The application brush part 3 is provided with the cutaway portions 32 formed by longitudinally cutting away some sections of the application portion 7 symmetrically with each other. That is, in view of the four directions in the cross section of the application brush part 3 , the application brush part 3 is provided with the cutaway portions 32 in the north and south directions and with the existing sections of the application portion 7 in the east and west directions.
A section of the application portion 7 fixed to the lowest end of the rod 21 through the initial twisting of the wire parts is removed so that the ring 22 can be exposed at the lowest end of the rod 21 . With the ring 22 , the application brush part 4 to be described later is coupled to the application brush part 3 .
FIG. 14 a is a front view of the application brush part, and FIG. 14 b is a sectional view taken along line B′-B′ of FIG. 14 a.
The arrangement brush part 4 comprises a cylindrical fixing stand 90 , and combs 8 formed on a side surface 91 of the fixing stand 90 .
The fixing stand 90 takes the shape of a cylinder with a length identical with or slightly shorter than that of the application brush part 3 , and is formed with a central insertion bore 92 longitudinally therethrough so that the rod 21 of the application brush part 3 can be inserted into the insertion bore 92 to cause the fixing stand to be coupled to the application brush part 3 . The side surface 91 of the fixing stand 90 is formed with open windows 94 perforated up to a lower end of the side surface such that when the fixing stand is coupled to the application brush part 3 with the cutaway portions 32 symmetrically formed therein, the existing sections of the application portion 7 of the application brush part 3 protrude outwardly through the windows. A protruding, coupling piece 95 that is to be fixedly inserted into the ring 22 of the rod 21 is formed at the lower end of the side surface 91 .
More specifically, the side surface 90 of the fixing stand 90 is divided into both lateral symmetric regions due to the formation of the open windows 94 . Lower ends of the both lateral regions of the side surface 91 are connected to each other via a support 96 . The coupling piece 95 is formed to protrude transversely and perpendicularly from the support 96 .
That is, in view of the four directions in the cross section of the fixing stand 90 , the open windows 94 of the fixing stand 90 are formed symmetrically in the east and west directions, and the combs 8 are formed symmetrically in the north and south directions on the side regions of the side surface 91 of the fixing stand 90 . The coupling piece 95 is formed to protrude from a side of the support 96 , which connects the side regions of the side surface 91 to each other, at a right angle with respect to the combs 8 formed on the side regions of the side surface.
Therefore, in order to couple the arrangement brush part to the application brush part as shown in FIG. 15 a, the insertion bore 92 of the fixing stand 90 is fitted around the rod 21 , and at the same time, the cutaway portions 32 of the application brush part 3 are placed at closed regions of the side surface 91 of the fixing stand 90 while the existing sections of the application portion 7 of the application brush part 3 are placed in the open windows 94 of the fixing stand 90 . Then, the coupling piece 95 of the fixing stand 90 is fixedly inserted into the ring 22 of the rod 21 that has been lowered up to the lower end of the fixing stand 90 through the insertion bore 92 . As shown in FIG. 15 b, the existing sections of the application portion 7 of the application brush part 3 are placed symmetrically in the east and west directions of the brush rod 2 , and the combs 8 of the arrangement brush part 4 are placed symmetrically in the north and south directions of the brush rod 2 .
FIG. 16 a shows a fifth embodiment of the present invention, in which an application portion 7 of an application brush part 3 is injection molded from a synthetic resin.
More specifically, a lower end of a brush rod 2 has a rod 21 extending therefrom, which has a diameter and length identical with that of the metal wire rod 21 of the previous embodiments. The application portion 7 for applying the mascara liquid to the eyelashes is radially formed on an outer circumferential surface of the rod 21 . The rod 21 is made of the same synthetic resin as the brush rod 2 , e.g., polyamide. The application portion 7 formed on the outer circumferential surface of the rod 21 is also made of the same material as the rod 21 by means of injection molding using a precision mold.
Further, a side surface of the rod 21 is formed longitudinally (perpendicularly to the cross section of the application brush part) with the cutaway portion 31 by cutting away a section of the application portion 7 , as shown in FIG. 16 b. At this time, the cutaway portion 32 is formed by longitudinally cutting away a section of the application portion 7 within an angular range of about 30 to 120 degrees about the center of the cross section of the application brush part 3 .
Accordingly, the fixing stand 40 of the arrangement brush part 4 used in the first embodiment can be coupled to the application brush part 3 with the application portion 7 formed on the outer circumferential surface of the rod 21 to form a mascara brush 1 , thereby applying the mascara liquid to the eyelashes.
Alternatively, as shown in FIG. 16 c, the cutaway portions 32 are formed symmetrically such that both sections of the application portion 7 formed at the both lateral sides of the rod 21 with respect to the cross section of the application brush part 3 are symmetric with each other. Thus, the fixing stand 50 of the arrangement brush part 4 used in the second embodiment can be coupled to the application brush part to form a mascara brush 1 .
Alternatively, the fixing stand 80 of the arrangement brush part 4 used in the third embodiment can be coupled to an application brush part 3 in which the cutaway portion 31 is formed at a side of the outer circumferential surface of the rod 21 by cutting away a section of the application portion 7 and the ring 22 is formed by perforating the lower end of the rod 21 , as shown in FIGS. 17 a and 17 b, thereby forming a mascara brush 1 .
Alternatively, the fixing stand 90 of the arrangement brush part 4 used in the fourth embodiment can be coupled to an application brush part 3 in which cutaway portions 32 are formed at both sides of the rod 21 by cutting away sections of the application portion 7 and the ring 22 is formed by perforating the lower end of the rod 21 , as shown in FIG. 17 c, thereby forming a mascara brush 1 .
In the mascara brush of the present invention, the application brush part for receiving a large amount of mascara liquid is formed at a side of the brush rod, and the arrangement brush part with the comb is formed at the other side of the brush rod. Thus, the mascara brush can performs two functions of application and arrangement by the single brush rod. Accordingly, it is possible to provide a mascara brush capable of ensuring more convenient make-up by allowing application of the mascara liquid (volume-up effect) and arrangement of eyelashes (curling, long lash and clean effects) at one time upon application of mascara to the eyelashes.
Further, in the case where one or more columns of combs are formed in the arrangement brush part, when the mascara liquid is applied by the application brush part and the eyelashes are then arranged by the arrangement brush part, the effects of volume-up, curling, long lash and clean can be obtained. Meanwhile, even when the mascara liquid is applied to the eyelashes by using only the arrangement brush part with the plurality of columns of combs, it is possible simultaneously to obtain a weak volume-up effect, and the effects of curling, long lash and clean.
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The present invention relates to a mascara brush. The present invention provides a mascara brush, wherein a single brush rod of the mascara brush is formed with both an application brush part with an application portion for applying a mascara liquid to eyelashes and an arrangement brush part with a comb for arranging the eyelashes in order to simultaneously perform the application of the mascara liquid and arrangement of the eyelashes, thereby conveniently imparting the effects of clean, long lash and curling to the eyelashes through a single process, the structure of the mascara brush is simplified so that a manufacturing process can be relatively simplified, and stability in use can be obtained due to the securely coupled state.
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BACKGROUND OF THE INVENTION
The present invention relates to a control system for a four-wheel drive vehicle for automatically changing the power transmission of the vehicle from two-wheel drive to four-wheel drive in accordance with road conditions.
In a conventional four-wheel drive vehicle, a power transmission system for a two-wheel driving is selectively changed to a four-wheel driving system by engaging a transfer clutch which is manually operated by a select lever.
For example, when the vehicle travels on slippery roads, such as snowy, sloppy or gravel road, by two-wheel driving, the transmission system should be changed to four-wheel drive in order to prevent the driving wheels from slipping. If this changing operation is done after the slipping occurs because of the driver's misjudgment of the slipping, the slipping cannot be stopped or reduced.
In order to resolve such a problem, an automatic control system for the four-wheel drive system has been proposed. The conventional system is provided with a slip detecting circuit which produces a clutch signal when the difference between the speed of the front and rear wheels exceeds a predetermined reference value. The clutch signal causes a clutch to engage, so that the transmission system is automatically changed to four-wheel drive.
However, since the automatic control system detects the slipping which already has occurred, the occurrence of slipping can not be prevented. Accordingly, such an automatic control system is not effective to prevent the slipping of wheels.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a system which detects slippery roads before a motor vehicle reaches the slippery roads in order to prevent the slipping of the wheels of the motor vehicle.
According to the present invention, there is provided a system, which comprises means for transmitting a high frequency wave to a surface of a road in front of a vehicle, means for receiving the reflected high frequency wave, comparing means for comparing the received wave with the transmitted wave and for producing an output dependent on the difference between amplitudes of both of the waves, and control means responsive to the output from the comparing means for engaging a clutch for providing four-wheel drive when the output exceeds a predetermined value.
The other objects and features of this invention will be apparently understood by way of example from the following description with reference to the accompanying drawings.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a schematic view showing an automatic transmission to which a control system according to the present invention is used;
FIG. 2 is a block diagram showing an electric circuit provided in the system of the present invention;
FIGS. 3a nd 3b show a circuit of the system shown in FIG. 2;
FIG. 4 shows transmitting and receiving waveforms;
FIG. 5 shows waveforms in the circuit of FIGS. 3a and 3b;
FIGS. 6a and 6b show another embodiment of the present invention; and
FIG. 7 shows waveforms in the circuit of FIGS. 6a and 6b.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, a crankshaft 1 of an internal combustion engine E mounted on a front portion of a vehicle is operatively connected with a torque converter 2 of an automatic transmission A.
The automatic transmission A comprises the torque converter 2, an automatic transmission device 4, and a final reduction device 14 for front wheels F of the vehicle.
The torque converter 2 comprises a pump impeller 2a and a turbine 2b. The pump impeller 2a is connected with the engine crankshaft 1. A turbine shaft 3 extends from the turbine 2b to the automatic transmission device 4.
The automatic transmission device 4 comprises a planetary gear 5, clutches 6 and 7 for selectively transmitting the output of the turbine shaft 3 to the planetary gear 5, by selectively locking a one-way clutch 8, a brake 9 and a brake band 10.
The output of the automatic transmission device 4 is transmitted to an output shaft 11 on which a drive gear 12 engaged with a driven gear 13 is securely mounted. The driven gear 13 is securely mounted on a shaft 16, on one end of which a drive pinion 17 is formed. The drive pinion 17 engages with a crown gear 15 of the final reduction device 14 for the front wheels F. The other end of the shaft 16 is connected to a transfer drive shaft 18 which extends rearwardly and is connected to a first transfer gear 20 of a transfer device 19. The first transfer gear 20 is engaged with a second transfer gear 21. The second transfer gear 21 is rotatably mounted on a rear drive shaft 23. A fluid-operated friction clutch 22 of the multiple-disc type is mounted on the rear drive shaft 23 for engaging the gear 21 with the shaft 23. The rear drive shaft 23 is further operatively connected to a final reduction device 25 for rear wheels R of the vehicle through a propeller shaft 24.
A pressure chamber 22a of the clutch 22 is communicated with an oil pump 26 through a passage 28, a solenoid-operated changeover valve 27 and a passage 28a. The changeover valve 27 has an inlet port 29 connected to the oil pump 26, an outlet port 30 connected to the pressure chamber 22a, and a drain port 31.
A spool 34 is operatively connected to a solenoid 32 and biased to the right by a spring 33. When the solenoid 32 is de-energized, the spool 34 is pressed by the spring 33 to close the inlet port 29 and to communicate the outlet port 30 with the drain port 31 as shown in FIG. 1. By draining the pressure chamber 22a, the clutch 22 disengages. When the solenoid 32 is energized, the spool 34 is shifted to the left to close the drain port 31 and to communicate the pressure chamber 22a with the oil pump 26 through the passage 28, ports 30, 29 and the passage 28a. Thus, the clutch 22 engages, thereby connecting the gear 21 with the shaft 23 to establish a four-wheel drive power transmission.
Referring to FIG. 2 showing the system of the present invention, a manual switch 36 is mounted on a select lever 35 of the automatic transmission device 4 and electrically connected in series between the solenoid 32 and a battery 37. Further, an electrically operated switch 38 is connected in parallel to the manual switch 36. Thus, the solenoid 32 is energized by closing the switch 36 or 38 to establish the four-wheel drive.
The system is provided with a transmitting system for transmitting a high frequency wave such as a microwave, laser beam, and an ultrasonic wave, and with a receiving system for receiving the high frequency wave. Referring to FIGS. 2 and 3a and 3b, the transmitting system comprises a high frequency sine-wave generator 42, an amplifier 43 and an antenna 40 for transmitting microwaves to the surface of the road at positions in front of the vehicle. The receiving system comprises an antenna 41 for receiving reflected waves from the road surface, and an amplifier 46. The output of the amplifier 46 is applied to a subtracting circuit 45 through an absolute circuit 44a where the output of the generator is converted to absolute value.
On the other hand, in order to delay the transmitting wave so its phase coincides with that of the received wave, the output of the wave generator 42 is applied to a phase-shifting circuit 47. The phase-shifting circuit 47 is applied with signals from an atmospheric pressure detecting circuit 48 and a temperature detecting circuit 49, so that the phase is corrected by signals therefrom. The output of the phase-shifting circuit 47 is applied to the subtracting circuit 45 through an absolute circuit 44. The output of the subtracting circuit 45 is applied to a comparator 50 through an absolute circuit 44b. The comparator 50 compares the input signal with a reference value from a reference voltage generating circuit 51. The output of the comparator 50 is applied to a driver 53 for the switch 38 through a holding circuit 52. The holding circuit 52 comprises a one-shot multivibrator 52b operated by the output signal of the comparator 50, an inverter 52c connected to the multivibrator 52b, and an OR gate 52a applied with outputs of the comparator and the inverter. The driver 53 comprises an amplifier 53a and a transistor 53b for energizing a solenoid 38a for operating the switch 38.
In operation, when the switch 36 is opened to de-energize the solenoid 32, the pressure chamber 22a of the clutch 22 is drained to disengage the clutch. Thus, the vehicle is driven only by the two front wheels of the vehicle.
In FIG. 4(a) shows a transmitted microwave waveform and FIG. 4(b) shows a received waveform reflected from a flat dry road with a delay Δt. When driving on a snowy or sloppy road, the amplitude of the received wave A becomes large as shown in (c) compared with the transmitted wave B, which is caused by the fact that such roads have high reflectance. In case of a gravel road, the amplitude of the received wave C varies a lot as shown in (d), since the transmitted wave is irregularly reflected on the rugged surface of the road.
When driving on a dry road, the transmitted waveform is substantially equal to the received waveform in shape. Accordingly, the output of the subtracting circuit 45 is zero, so that the output of the comparator 50 is at low level. When travelling on a slippery road, the subtracting circuit 45 produces output pulses. In FIG. 5(a) shows an example of input pulses B and D of the subtracting circuit 45. FIG. 5(b) shows the output (b) of the absolute circuit 44b and the reference value V 0 for the comparator 50. Thus, the comparator 50 produces pulses (c) as shown in (c), which causes the one-shot multivibrator 52b to operate to produce a continuous output. FIG. 5(d) shows the output (d) of the holding circuit 52. The output (d) is amplified by the amplifier 53a to turn on the transistor 53b. Thus, the solenoid 38a is energized to close the switch 38 to energize the solenoid 32, so that the changeover valve 27 is operated to communicate the passage 28a with passage 28. Accordingly the clutch 22 engages, thereby establishing the four-wheel drive. After the vehicle passes through the slippery road, the output of the comparator 50 goes to a low level, thereby changing the transmission to the two-wheel drive system.
Referring to FIGS. 6a and 6b showing another embodiment of the present invention, the same parts of the system as the parts of FIGS. 3a and 3b are designated by the same references as FIGS. 3a and 3b. The output of the generator 42 is applied to a zero-crossing detector 61 through a filter 60. On the hand, the output of the amplifier 46 is applied to a zero-crossing detector 61a through a filter 60a. The outputs of the zero-crossing detectors 61 and 61a are applied to an EXCLUSIVE-OR gate 62, and the outputs of the zero-crossing detector 61 and the gate 62 are supplied to an AND gate 63. The output of the AND gate 63 is applied to the phase shifting circuit 47 through an integrator 64. The rest is the same as the system of FIG. 3.
In FIGS. 7(a) to (h) show waveforms at locations a to h respectively in FIG. 6. The phase of the received wave b is different from the phase of the transmitted wave a. The phase difference is detected by the gates 62 and 63 as shown in (g). The pulses g representing the phase difference are integrated as shown in (h) and the output thereof is applied to the phase-shifting circuit 47. The circuit 47 operates to shift the wave a to coincide in phase with the wave b.
In accordance with the system of FIGS. 6a and 6b, phase shifting is performed without an atmospheric pressure detecting circuit and a temperature detecting circuit.
While the presently preferred embodiments of the present invention have been shown and described, it is to be understood that this disclosure is for the purpose of illustration and that various changes and modifications may be made without departing from the scope of the invention as set forth in the appended claims.
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A system for controlling power transmission of a four-wheel drive vehicle having main driving wheels of the vehicle powered by an engine. A clutch transmits the power of the engine to auxiliary driving wheels of the vehicle so as to provide forward drive. A transmitter transmits a high frequency wave to a surface of a road in front of the vehicle and a receiver receives the reflected wave. A comparator is provided for comparing the received wave with the transmitted wave. When the difference between the amplitudes of both waves exceeds a reference value, a control circuit engages the clutch for the four-wheel drive.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention pertains to a pole mounting type of electrical distribution transformer such as used for converting a 13,200 volt A.C. input to a 240/120 volt, single phase A.C. output for domestic and other usage that will permit hand hole entrance for maintenance and repair work and also provide total safety protection when used with a suitable current limiting fuse from the standpoint of avoiding blow-out of the top end wall under a build-up of high, fault-produced, internal fluid pressure. A phase of the invention deals with an improved transformer casing that has a pre-shaped wall construction based on its being subjected to relatively high positive internal fluid pressure, and that will have a combined hand hole cover and a simple and highly effective pressure relief means capable of efficient operation between lower cut-off to materially higher internal fluid pressures.
2. Description of the Prior Art
In recent years there has been a growing problem in the construction of overhead pole type distribution transformers from the standpoint of the blowing-off of upper cover end walls under internal fluid pressures developed by over-pressure phenomena, such as caused by electric arcing and other electrical faulting. Such transformers are mounted near the top of utility poles in residential areas, thus they tend to menace both persons and properties, since oil or other content may be ejected to fall as a hot and possibly fiery rain on anything or anyone in the immediate vicinity. Although so-called bleeder or light duty valve means have been mounted on the side of transformer tanks or housings for normal relatively low pressure venting, such means has been found totally unsatisfactory from the standpoint of a sudden and particularly high fluid pressure generation within the transformer such as may occur due to a fault of electrical equipment therein.
A conventional end wall cover which is retained in position over the upper edges of the side wall of a tank or housing by a take-up clamping chime ring similar to those used on dry bulk storage drums, represents a type that is most likely to be dislodged with considerable force under such conditions. Such covers for pole type transformers are made removable, since there are no other openings to permit access to the inside of the housing for modifying internal connections, operating internal tap changing switches and, in general, for easy maintenance.
Another type of end wall cover is removably mounted over the upper edge of the side wall of a transformer housing by means of a centrally projecting lug bolt whose inner end is threaded into an integrally secured cross piece within the housing and which serves to draw up the cover to a tightened relation on the circumferential edge of the housing. Both of these constructions entail risk from the standpoint of cover blow-off under high or sudden internal fluid pressure applications, such as occur from a failure to relieve quickly arising pressure that develops rapidly within the casing due to a fault which may result from the formation of an electrical arc under the oil dielectric. Such an arc may be caused by insulation failure or the fusing-apart of wires within or near the transformer windings, such as may occur under adverse operating conditions or as a result of some defect. Cover end wall blowing may be due to a very rapid internal pressure rise that can lift the oil column and slam it against the cover, simultaneously producing a force in the opposite direction against the bottom of the tank or housing and as well as forces against its sides. A second type has a fairly slow rise which gradually builds up in the transformer top and results in a blown cover and/or a deformed tank. The fault may or may not cause vaporization of the oil within the air space above the normal dielectric level therein.
As above indicated, side mounted relief devices have been provided to act as safety valves against normal pressure build-ups, such as due to loading and overloading of transformers. These valves are relatively small and inadequate to effectively relieve rapid build-up of pressure such as may occur as when internal arcing is present. There has been a need for an improved type of transformer tank or housing construction which can be relatively inexpensively produced and which will meet the problem involved in previous constructions, particularly from the standpoint of preventing high pressure dislodgement of the upper end wall and, in general, pressure deformation of a transformer tank or housing and, at the same time, which will permit entry to the inside of the casing for maintenance and repair of the electrical equipment therewithin.
SUMMARY OF THE INVENTION
It has thus been an object of the invention to provide an improved and more efficient enclosure construction for an overhead or pole type of transformer, particularly from the standpoint of providing a safe and sure type of venting or relief of fault-produced internal pressure build-up.
Another object of the invention has been to develop a new and and improved form of casing or housing construction for an overhead type of dielectric containing electrical transformer which will be effective to relieve normal minor operating fluid pressure and which, at the same time, under emergency conditions of high pressure build-up, will provide immediate and effective pressure relief without damaging its casing, blowing its end wall cover, and spewing hot fluid such as oil therefrom.
A further object of the invention has been to provide a transformer casing which may be substantially integral throughout its construction and will thus not require separate grounding connections as between its top end wall and its main cylindrical body, and which will enable a combined maintenance entry to its interior and a safety venting under high pressure build-up.
A further object has been to provide a transformer installation that in combination with a current limiting input fuse will assure a fully effective blow-off protection against fault-generated internal pressure.
A still further object of the invention has been to provide a practical, removable hand hole cover and safety relief construction for utilization with an enclosing upper end wall of an electrical transformer.
These and other objects of the invention will appear to those skilled in the art from the illustrated embodiment and the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view in elevation of a transformer devised and constructed in accordance with the invention;
FIG. 1A is a circuit diagram showing the use of at least one current limiting fuse in the transformer input circuit;
FIG. 2 is a top plan view of the transformer of FIG. 1 and on the same scale as FIG. 1;
FIG. 3 is an enlarged fragmental side section in elevation taken along line III--III of FIG. 2;
FIGS. 4, 5 and 6 are side sectional details in elevation on a greatly enlarged scale, particularly illustrating the construction and utilization of a combined pressure relief and hand-hole cover of the invention;
Specifically, FIG. 4 shows a tilted and slightly separated relation of the parts of the cover assembly that may be employed when the assembly is being inserted or removed from within an open entry end portion of the integral end wall;
FIG. 5 is illustrative of an adjusted, fully mounted position of the cover assembly at which its spring means is set to provide a tension closing action that is based on the force at which it is desired to have the cover assembly open to relieve internal fluid pressure;
FIG. 6 is illustrative of a uniform full opening of the cover member assembly, as effected by compressing the spring under force exerted internally of the transformer housing, such as may be occasioned by arcing within its chamber;
And, FIG. 7 is a fragmental section on the scale of and taken along line VII--VII of FIG. 5.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring particularly to FIGS. 1 and 2 of the drawings, an electrical power transformer unit A of an overhead or pole-mounting type is shown having a pair of high voltage input terminals B, and a group of side-mounted secondary or output terminals C. The unit A is shown provided schematically with a primary transformer winding D and a secondary winding E in a submerged relation within a dielectric liquid such as oil whose level is indicated as F. The hollow casing, housing or tank of the unit A has a cylindrical, upwardly extending, elongated side wall 10, and outwardly convex, integral, top and bottom end walls 11 and 12. It will be noted that end walls 11 and 12 are shown integral with and hermetically sealed with respect to the side wall 10 by continuous weld beads w (see FIG. 1). The side wall 10 has an angle-shaped, upper rim flange 10a whose inclined, inturned, uppermost portion serves as a receiving face for a complementary-shaped, outwardly sloped, over-fitting, mounting flange or rim 11a of the upper end wall 11 (see FIG. 3). Also, the side wall 10 has a circular, downwardly extending flange portion 10b of at least the full depth of the convex curvature of the bottom end wall 12. The outward convex shape of the angle-shaped mounting flange 11a, as well as the outward convexity of the side wall 10 and the end walls 11 and 12 provide a container construction of generally outwardly convex curvature that is able to withstand internal pressure forces that may otherwise tend to deform and thus weaken the casing or tank. The strength characteristics of the casing can thus be accurately predicted on the basis that fault-produced fluid pressure exerted internally against the wall, will have no deforming effect on its walls.
With particular reference to FIGS. 3 to 7, inclusive, the upper end wall 11 of the generally outwardly convexly shaped casing or tank of the unit A has a slightly sidewise-offset, open hole portion therethrough that provides a combined pressure relief and maintenance hand hole as defined by a seating flange 11b thereabout. As shown particularly in FIG. 3, the flange 11b is of angle-shape and has a horizontally planar underside portion a which is adapted to receive and position a cross-extending clamping member 30 (shown on channel-shape) to retain a cover assembly 15 in position with respect thereto. An innermost ring-like rim portion b of the flange 11b surmounts a horizontally planar upper seating face of ledge portion c that is in a direct parallel and opposed relation with respect to the underface a. When the cover assembly 15 is in a closed position such as shown in FIG. 3, the ledge portion c, in combination with the rim portion b, serves to receive and position a ring-like resilient seating gasket 17 of rectangular section thereon.
The assembly 15 has an outwardly convex or dome-shaped cover part or cap 16 that has a central opening therethrough to position and receive an operating stem 20. The cover 16 has a sealing flange portion 16a which on its underside is horizontally planar in a complementary manner with respect to the opposed upper face c of the flange 11b, and which is downwardly surmounted by a rim edge portion to receive and cooperate with the gasket 17. The gasket 17 may be cemented to either the under surface of flange 16a or to the upper face c of the flange 11b in such a manner that the opposed flanges will serve to provide a full closure of the open portion defined by the inwardly extending flange 11b of the end wall 11.
The operating stem 20 is carried for rotative movement with respect to the cover 16 by a bearing gasket 21 of a suitable relatively stiff resin material such as Teflon that is secured on the upper side of the cover. A handle portion, such as a cross bar or lever 22, is carried in a secured relation on the upper end of the stem 20 for manually rotating or turning it within and with respect to a nut 28 that is mounted on its lower threaded end portion 20a. The lower extent of the threaded portion 20a is sufficient to permit the cover assembly 15 to, as shown in FIG. 4, have its parts loosely retained in position with respect to each other for insertion and removal with respect to the open portion defined by the flange 11b. An end collar or flange 20b serves as a stop for limiting the maximum upward movement of the stem 20 within the nut 28 to thus prevent a separation of the cover assembly, such as may entail a fishing operation within the interior of the transformer tank.
Spring and clamping means is carried on the stem 20 and has a U-shaped bracket 27; the nut 28 is secured to an underside of its horizontal connecting portion, as by weld metal w. The bracket 27 has a pair of leg portions which extend upwardly from its central connecting portion to at least the height of the clamping member 30, in order to cooperate with opposite sides of the member 30 and prevent turning of the nut 28 when the stem 20 is being rotatably adjusted. The clamping member 30 which may also be a solid bar rather than a channel-shaped member, as shown particularly in FIGS. 6 and 7, is adapted at one end to abut against a downwardly projecting latching or stop lug or pin 13 that is shown welded to the underside portion a of the flange 11b, see FIGS. 3 and 7. The pin 13 limits rotation of the member 30 during turning movement of the stem 20 and thus, indirectly prevents rotation of the nut 28 through the agency of the bracket 27 whose legs project upwardly on opposite sides of the member 30.
Spring means 25, shown as a so-called Belleville washer type, may also for example, comprise one or more concentric helical springs. The spring means 25 at its upper end engages the underside of the clamping member 30 and its lower end may either directly engage the underside of the bracket 27 or engage abutment washer 26 that may be provided on the innerside of the connecting portion of the bracket 27. The spring means 25 is thus operatively positioned along the stem 20. When the stem 20 is, for example, rotated clockwise to effect upward rise of the nut 28 and the bracket 27 (see FIG. 6) by turning threaded portion 20a within the nut 28, a maximum compression force is exerted on the spring 25 that corresponds to the maximum normal operating pressure force to be permitted in the container or tank before it is released. It may, for example, be approximately 9 or 10 lbs./sq. in. The use of a lower force action eliminates any need for a conventional side-mounted relief valve; and rotating the stem 20 in the opposite direction to remove the cover 16 operates to bleed-off gas under moderate pressures below the operating pressure of the assembly.
The amount of potential tension force to be exerted by the spring means 25 is thus controlled by the upper extent of the threaded portion 20a. The operation of the assembly 15 is such that it will not only open at a set lower operating pressure force such as 9 to 10 lbs./sq. in., but will also immediately and effectively have a uniform opening cation under fault-generated high pressures of several hundred lbs./sq. in., to thus immediately relieve such pressure as it starts to build up and during its full period of exertion. This instant relief action prevents a large build-up of the pressure force which would tend to blow-off a cover or distort or damage the walls of the container.
The casing or tank of the unit A may be of any suitable material such as metal coated on the outside with a protective resin, the gasket 17 may be of a resilient resin or rubber-like construction, and the cover assembly 15 may also be of metal. It will be noted that the construction and operation of the cover assembly 15 is such that it will open substantially uniformly to define a fully circular opening to relieve pressure. Due to the operation of the spring means 25 the assembly 15 may be only slightly opened for normal operating low pressure release, but will be fully opened when the pressure is of a type such as generated by a transformer fault.
In the representative circuit diagram of FIG. 1A, a pair of high voltage input leads 31, 32 are shown connected to the primary D of the transformer unit A through at least one current limiting fuse 33. However, for maximized protection from the standpoint of a possible grounding, a second current limiting fuse 34 is shown. These fuses may be mounted outside the unit A. The output from the secondary E of the transformer is shown as consisting of leads 35, 36 and 37, with the lead 37 providing a neutral terminal that is grounded to the transformer casing consisting of side wall 10 and integral end walls 11 and 12.
By way of example, a pole type of transformer of the invention may be provided with a casing or tank designed to withstand about 200 lbs./square inch pressure. A typical transfer rate of efflux of about 60 cu. ft. per second atmospheric will result from an internal (tank) pressure of about 25 lbs./sq. inch gauge. The current limiting fuses 33 and 34 positioned outside the transformer may each have a current cut-off rating of or be set at about two times the current rating of the transformer. At least one such fuuse is important in limiting the period of fault-generated pressure build-up in the transformer to thus assure total blow-out protection. This protection not only applies to the blow-out of oil or dielectric fluid, but also of melted copper windings, paper and other material that may be activated by the transformer fault to seek release from the securely sealed or integral, closing-off side and top and bottom end walls of the transformer enclosure.
The exemplary so-called Belleville washer spring type is generically a tension-exerting stack of conical disc spring elements. A bell-mouthed shaped stacked spring assembly or any other suitable type of axially aligned tension-exerting spring may be employed for the spring means 25.
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A transformer is provided that utilizes a substantially fully integral, generally outwardly convex casing or tank for enclosing an electrical transformer in a dielectric environment. The casing has fully integral side and top and bottom end walls, and has an open portion in its top end wall of sufficient size to serve both as a positive low to high pressure release and a maintenance hand hole. An easily inserted and removed cover assembly employs an operating stem, a domed cover member, a clamping member, a nut carrying bracket member and a spring that may be adjusted to a desired pressure relief setting by rotating the stem in one direction. Rotation of the stem in an opposite direction releases its clamping setting and loosens the parts of the cover assembly in such a manner as to permit it to be easily and quickly removed from the open portion by tilting it with respect to and out of the open portion.
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CROSS REFERENCE TO RELATED APPLICATIONS
None. However, applicant filed Disclosure Document No. 079,501 on Apr. 2, 1979, which document concerns this application; therefore, by separate paper, it is respectfully requested that the document be retained.
BACKGROUND OF THE INVENTION
(1) Field of the Invention
This invention relates to vaporizing liquid fuels and mixing the vapor with air for spark ignition in an internal combustion engine.
(2) Description of the Prior Art
Automobiles are powered almost exclusively by internal combustion engines. With the advent of the energy shortage, people became concerned with the number of miles per gallon that their cars could get. Many cars on the road today have large engines which can produce much more power than is necessary to go the speed limit. These large engines use a great deal of gas. Many methods have attempted to increase the gas mileage of these large engines. These attempts to increase the performance of large engines have met with only varying degrees of success. One area for improvement is better vaporization of the liquid fuel. Different methods for controlling the amount of vapor have been tried. Many inventors have attempted to control the vapor flow by controlling the amount of fuel which is vaporized. This method is usually unsatisfactory as it is very difficult to regulate the rate of vaporization as opposed to the rate of introduction of the vapor into the carburetor.
Before filing this application, applicant caused a search of the prior art to be made at the U.S. Patent and Trademark Office. That search disclosed the following patents:
GRONKWIST--U.S. Pat. No. 1,625,997
MENGELKAMP--U.S. Pat. No. 2,821,843
AUTHEMENT--U.S. Pat. No. 3,963,013
PIERCE--U.S. Pat. No. 4,074,666
TOTTEN--U.S. Pat. No. 4,106,457
QUINN--U.S. Pat. No. 4,146,002
QUINN discloses a fuel preheater using hot water from the car's cooling system to vaporize fuel which is mixed with air and forwarded to the carburetor.
TOTTEN discloses a fuel vaporizer for vaporizing fuel using hot water and having a valve for adjusting the amount of fuel sent into the vaporizer.
It appears that the other patents listed are of general interest only. These prior patents show that the vaporization of gas and mixing it with air before it reaches the carburetor increases the gas mileage. However, one of the most perplexing problems has been the regulation of the flow of the vapor into the carburetor. Another problem in the art has been the maintenance of a steady heat in the vapor mixing compartment.
SUMMARY OF THE INVENTION
(1) New and Different Function
I have intended a way to improve the gas mileage which may be achieved with internal combustion engines. My invention does not increase the power of the engine, in fact, it is known that preheating the fuel-air vapor before it enters the engine has a tendency to reduce the total output of the engine. In view of the fact that automobiles on the road today have engines which generate far more power than is necessary for present speed limits, the increase in efficiency greatly outweighs the loss of power. I have found that great results are achieved when the introduction of the fuel vapor can be regulated.
My system vaporizes fuel at a rate greater than is necessary to be introduced into the carburetor. The amount of suction which is exerted on the fuel vapor line is varied by moving a vapor pickup either up or down in an air pickup tube of the carburetor. In this manner I am able to accurately control the amount of vapor introduced into the carburetor and thereby increase the total efficiency of the car's engine.
Thus it may be seen that the function of the total combination far exceeds the sum of the functions of the float valves, air filters, etc.
(2) Objects of this Invention
An object of this invention is to vaporize fuel for an internal combustion engine.
Another object is to vaporize fuel and thoroughly mix the vapor with air.
Further objects are to facilitate adjusting the flow of the vapor-air mixture into the carburetor.
Further objects are to achieve the above with a device that is sturdy, compact, durable, lightweight, simple, safe, efficient, versatile, ecologically compatible, energy conserving, and reliable, yet inexpensive and easy to manufacture, install, adjust, operate and maintain.
Other objects are to achieve the above with a method that is versatile, ecologically compatible, energy conserving, rapid, efficient, and inexpensive, and does not require highly skilled people to install, adjust, operate, and maintain.
The specific nature of the invention, as well as other objects, uses, and advantages thereof, will clearly appear from the following description and from the accompanying drawing, the different views of which are not scale drawings.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic representation showing the organization of the fuel vaporizer with an automobile engine.
FIG. 2 is a side elevational view of a vaporizer according to my invention.
FIG. 3 is a longitudinal section of the vaporizer generally along line 3--3 of FIG. 7.
FIG. 4 is a sectional view of the vaporizer taken substantially along line 4--4 of FIG. 3.
FIG. 5 is a top plan view of the backfire check valve.
FIG. 6 is a sectional view of the check valve taken substantially along line 6--6 of FIG. 5.
FIG. 7 is a top plan view of the vaporizer.
FIG. 8 is a sectional view of an air filter on the engine carburetor fitted with a fuel-air introduction unit according to my invention taken substantially on line 8--8 of FIG. 9.
FIG. 9 is a front elevational view of the fuel-air introduction unit with the air filter shown in section.
FIG. 10 is a sectional view of the fuel-air introduction unit taken substantially on line 10--10 of FIG. 8.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring more particularly to FIGS. 1 and 4 of the drawing, hot water is transmitted from the cooling system on engine or motor 16 (which includes radiator 10, water pump 14, and heater 32) through hot water line 12 to hot water inlet 18 of vaporizer 20. The hot water is introduced into hot water compartment 22 of the vaporizer. The top of hot water compartment 22 is formed by hot plate 24. Baffles 26 are located within the hot water compartment. The hot water is forced through the hot water compartment 22 among baffles 26 and out through return water outlet 28 back to the engine via water return line 30.
After the car's engine is warm, solenoid valve 34 may be electrically opened and solenoid valve 36 closed thereby diverting the liquid fuel from fuel line 38 to vaporizer inlet line 40 into fuel pool 42 in vaporizer compartment 120. The valve 34 may be eliminated and the inlet line 40 always be open. The level of the fuel in the pool 42 is controlled by fuel float 44 (FIG. 3).
The fuel inlet line 40 terminates at the valve 44.
When the fuel level drops, the valve is opened and more fuel enters the pool 42. Problems sometimes arise in the fuel float valve 44 so inspection plate 46, shown in FIG. 7, is located immediately above the float. By simply removing four screws, one may gain access to the valve 44. Also, three surge retarders 48 are located in the pool 42 on hot plate 24. The surge retarders are pieces of pipe with a plurality of holes spaced therein. These surge retarders 48 maintain the temperature stability and level of the fuel within the pool as well as helping to prevent unwanted sloshing of the fuel. The surge retarders 48 also help retain heat in the pool making the fuel vaporize more readily.
Heat radiates from the hot plate 24 heating some of the fuel in the pool to a vapor state. The fuel vapor then rises from vapor compartment 120 either through holes 50 or through vapor conduit 52 into vapor mixture compartment 54. Outside air enters the vaporizer 20 through an air inlet system. As air enters the inlet system it passes through vaporizer air filter 56 and proceeds through air inlet 58 into fan cage 60. Fan 62 is rotated by fan motor 64. Air from the fan cage is channelled through bifurcated air conduit 66 either into the vapor compartment 120 or into vapor mixture compartment 54. The fan 62 fully ventilates the vapor-air mixture. The vapor-air mixture is transmitted through vapor outlet 68 through vapor line 70 to the carburetor 72.
Check valve 74 is located below vaporizer air filter 56 in the air conduit 58. The check valve, shown in FIGS. 5 and 6, has two discs, upper disc 76 and lower disc 78. Lower disc 78 is suspended by piston 80 below the upper disc. The lower disc has a diameter less than the diameter of air conduit 58 while the upper disc 76 has a diameter equal to the diameter of the air conduit 58. Upper disc has five check valve holes 82 arranged around the termination 84 of the piston. In the operating, down position, air passes through holes 82 and around the perimeter of lower disc 78 into the fan cage 60. In the case of a backfire, the lower disc 78 is forced up against the upper discs 76 effectively closing the air supply into and out of the air conduit 66 from the fan 62. Spring 85 holds the lower disc 78 up in the closed position when there is no air flow as seen by the arrows in FIG. 6. This prevents the flow of vapors through the filter 56 when the engine is stopped.
Carburetor air filter 86 is fitted for vapor pickup 88. Vapor line 70 terminates in vapor pickup 88 and it is through this pickup that the air-fuel vapor is introduced into the carburetor 72. The vapor pickup is an "L" shaped tube which extends down through the air filter top 90 and at right angles into air pickup tube 92. The diameter of the vapor pickup 88 is about 1" (2.54 cm) and its distal end 94 is cut diagonally at 45°. An adjusting ear 96 is attached to the vapor pickup 88 at the bend in the "L." Adjusting rod 98 extends from the top of vacuum chamber 100 through air filter top 90 and through adjusting ear 96. The upper end of the adjusting rod 98 is threaded and the lower end is attached as by welding to the top of the vacuum chamber 100. Air is sucked into the carburetor 72 through air pickup tube 92. The air pickup tube 92 is tubular in shape and extends inward in the vacuum chamber toward the carburetor 72. The diameter of the air pickup 92 is about twice the diameter of the vapor pickup 88. The air pickup 92 has an opening end 102 and terminating end 104. Vapor pickup 88 enters the air pickup 92 at a right angle from the top, midway between the opening end and the terminating end. The diagonal cut at the distal end 94 opens toward the carburetor, i.e., down stream.
Flap 95 is pivoted by pin 97 in front of the opening end 102 of the air pickup tube 92. Wire or cable 99 extends from the flap 95. It may be seen that the flap 95 does not entirely cover the opening 102, so that always there is an air passage through it. However, flap 95 can greatly cut down the size of the opening. Those with ordinary skill in the art will understand that when the flap 35 blocks most of the opening 102 of the tube 92 that a richer fuel-air mixture will be introduced to the engine, i.e. that most of the gases entering the engine will be introduced from the vapor pickup 88. However, if the flap 95 is entirely removed from the opening 102 that a leaner fuel-air mixture will be introduced inasmuch as more air will come from within the air filter 86. The control wire 99 may be operated manually or by automatic means.
The amount that vapor pickup 88 extends down into the air pickup 92 may be adjusted by moving nuts 106 and 108. Adjusting nut 106 is located below adjusting ear 96 and may be raised or lowered on the threads of adjusting rod 98. Lock nut 108 locks the ear into position when it is tightened down on adjusting nut 106 and adjusting ear 96. By raising or lowering the vapor pickup 88, the amount of vapor which is sucked into the carburetor may be regulated. As the vapor pickup 88 is lowered further into the air pickup, the suction from the carburetor is greater. This greater suction draws more of the air-fuel mixture from the vaporizer into the carburetor. By raising nut 106 on the threads of adjusting rod 98 and tightening nut 108 down over the adjusting ear 96, vapor pickup 88 is raised and the suction is less making the mixture introduced into the carburetor leaner. In this manner, the percentage of the air-fuel mixture introduced into the carburetor may be controlled and varied. While one type of air filter is shown in FIGS. 8 and 9, it is understood that this invention is applicable to all air filters commonly used on automobiles.
FIG. 1 also shows an alternative fuel supply to the carburetor. When the engine is cold a very rich air-fuel mixture is desired and so fuel may be sent directly to the carburetor without being vaporized. Under this circumstance, fuel goes from the fuel pump through the fuel line 38 to the carburetor. Whether fuel travels directly to the carburetor or through the vaporizer is controlled by solenoid valves 34 and 36. Solenoid valve 36 is in fuel line 38 while solenoid valve 34 is in vaporizer line 40. When solenoid 38 is open, solenoid valve 34 is closed and vice versa.
The vacuum chamber 100 is held in place by thumb nut 110 upon carburetor rod 112. The chamber is sealed by sponge rubber gasket 114 to the bottom 116 of the filter. The filter is held firmly on the carburetor by thumb nut 118 upon the carburetor rod 112.
The embodiment shown and described above is only exemplary. I do not claim to have invented all the parts, elements or steps described. Various modifications can be made in the construction, material, arrangement, and operation, and still be within the scope of my invention. The limits of the invention and the bounds of the patent protection are measured by and defined in the following claims. The restrictive description and drawing of the specific example above do not point out what an infringement of this patent would be, but are to enable the reader to make and use the invention.
As an aid to correlating the terms of the claims to the exemplary drawings, the following catalog of elements is provided:
______________________________________10 radiator 70 vapor line12 hot water line 72 carburetor14 water pump 74 check valve16 motor 76 upper disc18 hot water inlet 78 lower disc20 vaporizer 80 piston22 hot water compartment 82 check valve hole24 hot plate 84 piston termination26 baffles 85 spring28 return water outlet 86 air filter, carburetor30 water return line 88 vapor pickup32 heater 90 air filter top34 valve, vapor 92 air pickup tube36 valve, liquid 94 vapor pickup distal38 fuel line 95 flap40 vaporizer inlet line 96 adjusting ear42 pool 97 pin44 fuel float valve 98 adjusting rod46 inspection plate 99 cable48 surge retarders 100 vacuum chamber50 holes 102 air pickup opening end52 vapor conduit 104 air pickup terminating end54 vapor mixture compartment 106 adjusting nut56 vaporizer air filter 108 lock nut58 air inlet 110 thumb nut60 fan cage 112 rod, carburetor62 fan 114 gasket64 fan motor 116 bottom66 air conduit 118 thumb nut68 vapor outlet 120 vapor compartment______________________________________
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Hot water is transmitted from an automobile's cooling system to a fuel vaporizer wherein it is used to heat gasoline to a vapor state. Air is added to the vapor by a fan, then forced to the carburetor. The flow of vapor into the carburetor is controlled by adjusting a vapor pickup within the carburetor's air cleaner. In this manner, the fuel-air vapor is more efficiently burned in the engine and better mileage is achieved.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application Ser. No. 60/589,192 filed Jul. 19, 2004 which is incorporated by reference herein in its entirety.
FIELD OF THE INVENTION
[0002] The present invention pertains to communication systems for use with moving vehicles and in particular to moving vehicles undergoing speed detection utilizing an external probing signal.
DESCRIPTION OF THE RELATED ART
[0003] With increasing miniaturization of electronics, vehicles are being provided with an ever widening array of information systems. Mapping and position detecting systems, for example, provide the motorist with important data which must be continuously updated. Detection systems have long been popular with motorists to provide an electronic early-warning of near by speed detection units. Such systems provide either proximity sensing for surrounding speed detection activity or detection of probing signals directed to the motorist's vehicle. Today, speed detection systems monitor traffic from both radar emitting and laser emitting probing systems of the type used by various law-enforcement agencies to sense and gauge the speed of passing motor vehicles. Traditionally, the range of the typical radar-sensing device exceeds that of most probing devices, thus providing an early warning to motorists of the presence of probing activities. Typically, the warning is early enough to provide a motorist ample time to monitor and adjust vehicle speed, if necessary, before entering the effective operating range of a probing site.
[0004] In typical speed detection systems, an antenna and receiver is mounted at the front most portion of the vehicle, the location most likely targeted by probing signals. Electronic processing of the signals is required before being presented to the motorist at a location within the passenger compartment adjacent the driver's position. Electronic circuitry for processing the received signals and providing the motorist with an indication of various aspects of speed detecting activity can be located at the front end of the vehicle, in the engine compartment or in the passenger compartment. It has been necessary to run wiring from the antenna/receiver to the various components and ultimately to a destination adjacent the driver's position. Routing of wiring is costly, especially so if great care is taken to avoid cluttering the appearance of the motor vehicle. Appearance problems are aggravated in ever increasing ways by the growing number of aftermarket onboard vehicular electronic systems being offered today. As wiring is secreted deeper and deeper within the vehicle so as to remain out of site, there is a possibility that pinch points and other types of wiring-degrading situations will be encountered, compromising the functional integrity of the installed system. Accordingly, labor and other installation costs for speed detection and other onboard systems which must communicate throughout the length of the vehicle is becoming increasingly costly, even to the point of approaching or perhaps exceeding the cost of the system electronics and hardware.
SUMMARY OF THE INVENTION
[0005] It is an object of the present invention to provide communication systems which extend throughout substantial portions of a vehicle's length. More specifically, it is an object of the present invention to provide communication systems which extend from the front end of the vehicle, through the engine compartment and firewall to the passenger compartment, to a location in or under the dash adjacent the driver's seat.
[0006] Further, it has been found important in providing improved detection of speed sensing activity, that antennas and signal receivers be located at both the front end and rear end of the vehicle. Accordingly, communication signals for the systems must travel throughout the length of the vehicle, being presented to the motorist adjacent the driver's seat. While the placement of special wiring to the rear end of a front engine vehicle may be somewhat less complicated than wiring extended through the engine compartment, great care must still be taken if unsightly alteration of the vehicle is to be avoided. Accordingly, another object of the present invention is to provide communications systems extending from either the front or the rear end of the vehicle without requiring dedicated addition wiring. More particularly, it is an object of the present invention to provide wireless communications systems or to adapt existing wiring runs extending from the front end and/or rear end of the vehicle to a position adjacent the driver's seat.
[0007] In one embodiment of a communication system is provided for a vehicle traveling over a road surface and having a front end, a forward compartment, a passenger compartment, a wall dividing the forward compartment and the passenger compartment, and a rear end. A detector is provided at the front end for sensing speed detection signals impinging on said vehicle, to monitor the speed of said vehicle or a nearby vehicle and to generate an output signal in response thereto. A radio frequency transmitter is provided adjacent the front end for receiving said detector output signal and for transmitting a transmit signal indicative of said speed detection signals in response thereto directed toward said road surface so as to be deflected toward the passenger compartment. A receiver is provided adjacent said wall, either in said front compartment or in said passenger compartment, for receiving said transmit signal from the road surface and for outputting an annunciator signal in response thereto. An annunciator is provided in the passenger compartment, coupled to said receiver to receive said annunciator signal and for outputting an annunciator indication in response thereto.
[0008] In another embodiment, a communication system is provided for a vehicle traveling over a road surface and having a front end, a forward compartment, a passenger compartment, a wall dividing the forward compartment and the passenger compartment, and a rear end. A detector is provided at the front end for sensing speed detection signals impinging on said vehicle, to monitor the speed of said vehicle or a nearby vehicle and to generate an output signal in response thereto. A radio frequency transmitter is provided adjacent the front end for receiving said detector output signal and for transmitting a transmit signal indicative of said speed detection signals in response thereto. A receiver is provided adjacent said wall, either in said front compartment or in said passenger compartment, for receiving said transmit signal and for outputting an annunciator signal in response thereto. An annunciator is provided in said passenger compartment, coupled to said receiver to receive said annunciator signal and for outputting an annunciator indication in response thereto.
[0009] Any further embodiment, a communication system is provided for a vehicle traveling over a road surface and having a front end, a forward compartment, a passenger compartment, a wall dividing the forward compartment and the passenger compartment, a rear end and wiring from the front and rear ends to the passenger compartment carrying signals unrelated to monitoring of the speed of the vehicle. A detector is provided at the front end for sensing speed detection signals impinging on said vehicle, to monitor the speed of said vehicle or a nearby vehicle and to generate an output signal in response thereto. A radio frequency injector is provided adjacent the front end for receiving said detector output signal and for injecting a transmit signal indicative of said speed detection signals in response thereto on said wiring for delivery to said passenger compartment. A receiver is operatively associated with said wiring for receiving said transmit signal and for outputting an annunciator signal in response thereto. An annunciator is provided in said passenger compartment, coupled to said receiver to receive said annunciator signal and for outputting an annunciator indication in response thereto.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] In the drawings:
[0011] FIG. 1 is a perspective view of a vehicle incorporating a communications system according to principles of the present invention;
[0012] FIG. 2 is a perspective view similar to FIG. 1 , but where communication paths are contained within a vehicle body;
[0013] FIG. 3 is a cross-sectional view taking along the line 3 - 3 of FIG. 1 ;
[0014] FIG. 4 shows the front portion of FIG. 3 , taken on an enlarged scale;
[0015] FIG. 5 is a perspective view of a vehicle having an alternative communications system according to principles of the present invention;
[0016] FIG. 6 is a fragmentary cross-sectional view of a vehicle having an alternative communications system according to principles of the present invention;
[0017] FIG. 7 is a schematic block diagram of the remote unit portion of the communications system;
[0018] FIGS. 8 a and 8 b together comprise a schematic block diagram of the control unit portion of the communications system;
[0019] FIG. 9 is an electrical schematic diagram of the control unit of FIG. 7 ;
[0020] FIG. 10 is an electrical schematic diagram of the control unit of FIGS. 8 a and 8 b;
[0021] FIG. 11 is an electrical schematic diagram of the voice input portion of the control unit of FIG. 10 ;
[0022] FIG. 12 is an electrical schematic diagram of the voice output portion of the control unit of FIG. 10 ;
[0023] FIG. 13 is an electrical schematic diagram of a programming interface between the remote and controlled units;
[0024] FIG. 14 is a perspective view of the remote unit from one end thereof;
[0025] FIG. 15 is a perspective view of the remote unit from an opposite end thereof shown with the communication module omitted;
[0026] FIG. 16 is a schematic flow diagram of a host Bluetooth start-up and initialization routine;
[0027] FIG. 17 is a schematic flow diagram of a host Bluetooth wireless communications link routine;
[0028] FIG. 18 is a schematic flow diagram of a remote Bluetooth start-up and initialization routine;
[0029] FIG. 19 is a schematic flow diagram of a remote Bluetooth wireless communication line routine;
[0030] FIG. 20 a - 20 c together comprise a schematic flow diagram of a start-up main processing loop routine;
[0031] FIG. 21 is a schematic flow diagram of a host PIC initialization routine;
[0032] FIGS. 22 a and 22 b together comprise a schematic flow diagram of an incoming voice command processing routine;
[0033] FIG. 23 is a schematic flow diagram a front remote alert routine;
[0034] FIG. 24 is a schematic flow diagram of rear remote alert routine;
[0035] FIG. 25 is a schematic flow diagram of a general system timing routine;
[0036] FIG. 26 is a schematic flow diagram of a remote data receiving routine;
[0037] FIGS. 27 a - 27 c together comprise a schematic flow diagram of a remote data processing routing;
[0038] FIG. 28 is a schematic flow diagram of remote PIC radar polling and processing routine;
[0039] FIG. 29 is a schematic flow diagram of a remote PIC laser polling and processing routine;
[0040] FIG. 30 is a schematic flow diagram of a remote PIC initialization routine;
[0041] FIG. 31 is a schematic flow diagram of PIC interrupt service routines for low power and normal operation modes;
[0042] FIG. 32 is an exploded perspective view of the wireless control unit;
[0043] FIGS. 33 a and 33 b together comprise an electrical schematic diagram of the wireless control unit;
[0044] FIG. 34 is a first sequence diagram illustrating operation of the wireless control unit; and
[0045] FIG. 35 is a second sequence diagram illustrating operation of the wireless control unit.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0046] As will be seen herein, the present invention is concerned with providing an early warning to a motorist of various surveillance and probing signals directed to the user's vehicle. While such detection systems can be quite simple, the more desirable systems sense a variety of different types of probing signals coming from different directions. The present invention is particularly directed to warning systems which are built into the vehicle in a manner so as to be inconspicious as possible. The present invention is concerned with eliminating additional wiring as may be required for a detecting system. As will be seen herein, the present invention contemplates wireless communication to throughout the vehicle and alternatively, adapting existing wiring not intended for use with detecting systems, which is nonetheless provided by the vehicle manufacturer. Accordingly, the communications systems according to principles of the present invention can be embodied in a variety of forms.
[0047] Referring now to the drawings and initially to FIGS. 1-4 , a motor vehicle 10 has a front end 12 and a rear end 14 . As is customary, the vehicle 10 is provided with bumpers at the front end and rear end and a license plate frame assembly 16 mounted to the front bumper is visible in the figures. Law enforcement officers and other people engaged in surveillance activities are typically taught to target the license plate when probing the vehicle. In the preferred embodiment, the license plate assembly 16 includes a laser detector and defuser module commercially available from the assignee of the present invention. In the preferred embodiment, a detector 18 for radar radiation is also provided and is located in a forward part of the vehicle, usually separate from the laser detector 16 . An additional detector is optionally installed at the rear of the vehicle.
[0048] Referring to FIGS. 14 and 15 , the radar detector 18 comprises a portion of a remote unit generally indicated at 20 . In FIG. 14 , the front face 21 of the radar detector 18 contains a radar receiving antenna, not visible in the figure. At the opposed end of remote unit 20 an interface or communication block 22 transmits radar detection signals to a control unit in or near the passenger compartment or cockpit. Referring to FIG. 15 , (which does not show block 22 ) a connector 24 provides local power to the radar detector 18 . One feature of the present invention is that the communication block 22 is retrofitted to existing radar detector units 18 , without requiring modification to the radar detector unit.
[0049] As mentioned, the license plate assembly 16 is typically chosen as a target for laser probing of the vehicle. The license plate is also typically chosen as a target point for radar probing signals although the radiation beam of the radar probing signals is typically much wider than that for laser probing signals. Also, the radar signals directed to adjacent vehicles and reflections from nearby objects may be sensed by the radar detector in vehicle 10 , thus providing useful information to the driver, in addition to radar probing signals directed specifically at vehicle 10 .
[0050] Referring to FIG. 4 , laser probing signals typically have a much smaller beam limited generally to the area of the license plate 32 . Frame work 34 surrounding the license plate contains active circuitry that responds to laser radiation and which emits a laser detecting signal carried on cable 26 , which is received on remote unit 20 . In FIGS. 1-5 , laser and radar detection signals are wirelessly transmitted to a receiver or control unit 36 located either outside the firewall 38 ( FIG. 2 ) or behind firewall 38 within the passenger compartment 40 (see FIGS. 1, 3 and 5 ). In FIG. 6 , laser and radar detection signals are impressed on existing power wiring 42 such as that installed by the vehicle manufacturer, and which is not intended for use with a detection system.
[0051] As shown in FIGS. 1-3 and 6 , the laser and radar detection signals are passed through a forward compartment 44 of vehicle 10 , located in front of passenger compartment 40 . With reference to FIG. 1 , vehicle 10 also includes a rear compartment 46 and a second remote unit 20 passes detector signals through rear compartment 46 to control module 36 located in the passenger compartment. The rear remote unit 20 is usually limited to reception of radar signals only. Thus, in the embodiment illustrated in FIG. 1 , vehicle 10 is said to be provided with forward and rearward looking radar detection capability. The communication system according to principles of the present invention conducts detecting signals from various sources over various paths to the receiver or control unit 36 which advises the driver of surveillance and probing activity, preferably via one or more annunciators. It should be noted that communication systems according to principles of the present invention work equally well for front engine, mid engine and rear engine vehicles. For purposes of explanation herein, it will be assumed that vehicle 10 is a front engine vehicle and that front compartment 44 contains the usual engine components, while compartment 46 at the rear of the vehicle comprises a conventional trunk space.
[0052] Referring again to FIGS. 14 and 15 , remote unit 20 includes communication block 22 . Other relative orientations of the radar receiving antenna and radio frequency transmitting antenna are possible. For example, in FIG. 5 the radio frequency transmitting antenna is transmitted in a sideways direction to bounce off of nearby objects so as to enter the passenger compartment 40 from the side. If desired, a radio receiver 54 can be located at the side of the vehicle for connection to control unit 36 with a relatively short wiring run 56 . Preferably though, the wireless communication path provided by the communication system accordingly to principles of the present invention traverses generally longitudinal paths from the front and rear of the vehicle to the passenger compartment or a firewall located adjacent a front or rear compartment.
[0053] Referring briefly to FIGS. 1 and 2 , the wireless communication paths are shown in the engine compartment 44 . As indicated, the communications paths of the radio frequency signals emitted from the remote unit 20 are reflected within the engine compartment, eventually passing to the control unit 36 . In FIG. 1 , one signal path 58 is reflected from the ground so as to be received at control unit 36 . This ground skip path comprises one of the paths of radiation emitted from remote unit 20 (and subsequently detected in a receiver). In FIG. 2 , it is assumed that no ground skip signal is present and that radiation of the wireless signal from remote unit 20 to control unit 36 is contained within vehicle 10 . In the arrangement of FIG. 2 , additional signals otherwise provided by ground skip paths are unavailable for improved detection capability by wireless receivers located in control unit 36 . In FIG. 2 , control unit 36 is located within the forward compartment 44 and is attached to firewall 38 or another convenient mounting site. In FIG. 1 , control unit 36 which receives the wireless signals is located behind firewall 38 , and passenger compartment 40 .
[0054] As will be appreciated by those skilled in the art, the firewalls of conventional vehicles are perforated with passageways for equipment and wiring and radio frequency signals can conveniently travel through these firewall openings (in addition to the ground skip paths, previously mentioned). If signal attenuation at the control unit 36 is excessive, the control unit can be mounted in the forward compartment, as shown in FIG. 2 , and relatively short wiring can pass through the firewall to visual and audible annunciators located within the passenger compartment. In the preferred embodiment, the radio frequency link between remote unit 20 and control unit 36 operates on a frequency approved for use by the Federal Communications System. Preferably, the radio link uses a 2.4 GHz carrier frequency although other carrier frequencies such as possible future frequencies in the unlicensed spectrum in the 450 MHz and 900 MHz bands could be used as well. In the present invention, a cost effective conventional interface is employed to ensure orderly and reliable transmission of data bits between remote units 20 and control unit 36 . It is generally preferred that the Bluetooth radio interface standard is employed, to accommodate optional features such as the wireless control unit to be described herein, and to take advantage of future integration opportunities with other motor vehicle devices. The invention contemplates other popular interfaces such as Wi-Fi, CDMA, TDMA, TDD, FDD and analog, for example.
[0055] One problem to be dealt with in a practical wireless link is a situation where two radio frequency signals or vectors arrive at the control unit at the same time. For example, one vector could bounce over the ground surface while another defector could bounce from surfaces of the vehicle. The Bluetooth interface standard preferred in the present embodiment has provision for distinguishing one simultaneous vector from another using a predetermined timing assignment. Once a vector is received with sufficient strength to be reliably demodulated, other vectors with the same time stamp are ignored. The ability to have additional vectors traveling along ground skip paths provides a substantial advantage in system operation and reliability. Also, wireless reception in the control unit 36 can be processed in no way such that an incoming signal is considered to be reliable only when multiple vectors carrying that signal are considered to be reliable. In this latter instance, the ability to receive the additional vectors traveling over ground skip paths can provide a substantial operating advantage.
[0056] Depending upon the path preferences within vehicle 10 , the antenna for transmitting radio frequency information from remote unit 20 can be tailored to prefer one communication path over another to avoid unusually strong attenuation circumstances which may arise due to vehicle construction. With the present invention, different communication blocks can be provided with the radar detector module at the time of installation, to customize the communication system for a particular vehicle.
[0057] Before proceeding to a more detailed explanation of the wireless embodiments of communications according to principles of the present invention, attention will be directed to FIG. 6 where existing vehicle wiring is adapted to provide a communication system for detection devices. In FIG. 6 , a remote unit 20 is connected to internal wiring 42 of the vehicle provided by the vehicle manufacturer, for delivering direct current power, for example. Radio frequency detection signals from the remote unit(s) 20 are impressed on the wiring which typically carries a direct current power signal. The radio frequency data is virtually identical to the radio frequency data in a wireless embodiment. Conventional equipment such as that provided by Cambridge Silicon Radio, Zeero or TI can be employed for this purpose.
[0058] Referring now to FIG. 7 , the remote unit 20 will be described in greater detail. Component 60 contains the radio interface protocols. The choice of protocols is independent and Bluetooth is selected for illustration because of its cable replacement use. The electronics component 60 obtains the electrical power necessary to operate by using power circuit 62 of conventional construction. The power circuit 62 is connected to a DC voltage source of 12 volt potential, capable of delivering a minimum current of 100 milliamperes. The connection is made through an external wire cable 65 shown in FIG. 14 which enters the internal components through communication block 22 . A controller is used to collect the output of the radar module 18 as indicated at 66 in FIG. 7 . The controller 66 preferably comprises a micro controller, catalog number PIC16F627-04I/SS, available from Microchip Technology located at Chandler, Ariz. Other types of controllers or microprocessors could be employed, as desired. The controller is chosen so as to accommodate the inputs 66 of the radar module and inputs 68 of the laser module. The radar and optionally laser detector signals are analyzed and sent along using one of the radio interfaces and vector paths between remote unit 20 and control unit 36 as indicated in the Figures. The software necessary to run the communication system of remote unit 20 is loaded through an interface using SPI techniques.
[0059] The control unit 36 uses the circuit depicted in block form in FIG. 8 (shown divided between FIGS. 8 a and 8 b for clarity). The radar detector data transmitted from remote unit 20 is received at host module 76 , via antenna 77 . The antenna 77 is internal to the body of the control unit and preferably comprises a surface mount component on the printed circuit board of the wireless control unit 36 so as to maintain a clean profile and to allow installation in the largest population of different vehicle configurations. Information received at host module 76 is passed along to a main control unit 78 , a micro controller, catalog number PIC16LF873A-I/SS from Microchip. The main control unit 78 processes received information and alerts the driver of the vehicle 10 by activating an appropriate light emitting diode 80 or 82 . In addition, a voice alert code is sent to an optional voice recognition unit 86 . The voice recognition unit 86 , when employed, preferably comprises a conventional voice recognition integrated circuit commercially available as part number RSC-4128 commercially available from the Sensory Company located at Santa Clara, Calif. The voice recognition unit 86 uses the code given by main control unit 78 to access a preprogrammed sound file and external EEProm 90 so as to play the appropriate message at speaker 92 . In the preferred embodiment, commands are given to the control system 36 by the driver, using vocal directives. Other input techniques known in the art, can also be used. In an optional control unit voice recognition capabilities are provided by voice recognition unit 86 , using microphone 94 . The voice commands delivered to the voice recognition unit 86 by the microphone are processed and matched according to values stored in the external memory unit 90 . If desired, the voice recognition unit can be omitted, for example, in favor of a wireless remote control unit 130 to be described later, herein.
[0060] More detailed electronic schematic diagrams for the remote and control units are given in FIGS. 9-13 . For example, module 60 of FIG. 7 which delivers data to transmitting antenna 61 is indicated in the electrical schematic diagram of FIG. 9 as module U 7 which preferably comprises a Bluetooth radio module, catalog number BC219159DN-E4 available from CSR located in Cambridge, UK. The PIC controller 66 in FIG. 7 is shown in FIG. 9 is commercially available as part no. PIC 16F627-041/SS from Microchip Technology of Chandler, Ariz. Data outputted from unit U 7 is transmitted via RF link 102 from controller 66 . Output signals are sent by control unit 66 in response to radar data signals on line 104 and laser data signals on line 106 coupled to the radar detector module 18 and laser detector module 16 respectively of FIG. 1 , for example. As noted in the bottom left corner of FIG. 9 , a connector 110 is provided for Bluetooth programming, using the interface circuit 112 shown in FIG. 13 which couples connector 110 to a connector 114 of FIG. 10 .
[0061] Referring now to the electrical schematic diagram of FIG. 10 , connector 114 is coupled to Bluetooth host module U 2 , which is identical to module 76 of FIG. 8 . Bluetooth module U 2 is coupled through UART Universal Asynchronous Receiver/Transmitter coupling 118 . This coupling is in turn terminated at terminals 120 of the PIC main controller 78 also shown in FIG. 10 . Output lines 122 from controller 78 energize light emitting diodes 80 , 82 . Voice commands from optional voice recognition unit 86 at FIG. 11 are received at input lines 126 of controller 78 as shown in FIG. 10 . Tones generated by controller 78 are outputted on lines 128 as shown in FIG. 10 so as to be received at input lines 131 in FIG. 12 . This tone generator data is processed and sent to speaker 92 in FIG. 12 . In the electrical schematic diagrams of FIGS. 11 and 12 , the same voice recognition unit 86 preferably comprises a voice processor chip, catalog number RSC-4128 Romless available from Sensory Inc. of Santa Clara.
[0062] The various control modules and voice recognition units must be programmed to function as described herein. Flowchart diagrams are given for the devices of various portions of the communication system in FIGS. 16-31 .
[0063] FIG. 16 is a schematic flow diagram of a host Bluetooth start-up and initialization routine. The code for this routine is stored in U 2 , ref # 92 , see FIG. 10 .
[0064] FIG. 17 is a schematic flow diagram of a host Bluetooth wireless communications link routine. The code for this routine is stored in U 2 , ref # 92 , see FIG. 10 .
[0065] FIG. 18 is a schematic flow diagram of a remote Bluetooth start-up and initialization routine. The code for this routine is stored in U 7 , ref # 47 , see FIG. 9 .
[0066] FIG. 19 is a schematic flow diagram of a remote Bluetooth wireless communication link routine. The code for this routine is stored in U 7 , ref # 47 , see FIG. 9 .
[0067] FIG. 20 a - 20 c together comprise a schematic flow diagram of start-up main processing loop routine. The code for this routine is stored in U 3 , ref # 78 , see FIG. 10 .
[0068] FIG. 21 is a schematic flow diagram of a host PIC initialization routine. The code for this routine is stored in U 3 , ref # 78 , see FIG. 10 .
[0069] FIGS. 22 a and 22 b together comprise a schematic flow diagram of an incoming voice command processing routine. The code for this routine is stored in U 10 , ref # 86 , see FIG. 11 .
[0070] FIG. 23 is a schematic flow diagram of a front remote alert routine. The code for this routine is stored in U 3 , ref # 78 , see FIG. 10 .
[0071] FIG. 24 is a schematic flow diagram of rear remote alert routine. The code for this routine is stored in U 3 , ref # 78 , see FIG. 10 .
[0072] FIG. 25 is a schematic flow diagram of a general system timing routine. The code for this routine is stored in U 3 , ref # 78 , see FIG. 10 .
[0073] FIG. 26 is a schematic flow diagram of a remote data receiving routine. The code for this routine is stored in U 3 , ref # 78 , see FIG. 10 .
[0074] FIGS. 27 a - 27 c together comprise a schematic flow diagram of a remote data processing routing. The code for this routine is stored in U 3 , ref # 78 , see FIG. 10 .
[0075] FIG. 28 is a schematic flow diagram of remote PIC radar polling and processing routine. The code for this routine is stored in U 8 , ref # 64 , see FIG. 9 .
[0076] FIG. 29 is a schematic flow diagram of a remote PIC laser polling and processing routine. The code for this routine is stored in U 8 , ref # 64 , see FIG. 9 .
[0077] FIG. 30 is a schematic flow diagram of a remote PIC initialization routine. The code for this routine is stored in U 8 , ref # 64 , see FIG. 9 .
[0078] FIG. 31 is a schematic flow diagram of PIC interrupt service routines for low power and normal operation modes. The code for this routine is stored in U 8 , ref # 64 , see FIG. 9 .
[0079] Referring now to FIGS. 8 a , and 32 - 35 , a wireless control unit 130 is provided to allow a user to wirelessly communicate with the warning system, without requiring extensive modification to the interior of the user's vehicle. As will be seen herein, the wireless control unit 130 allows a user to input commands to the warning system and to receive status indications of various portions of the system. Preferably, the wireless control unit 130 is Bluetooth enabled, operating as a remote module communicating with the aforementioned Bluetooth system which includes, for example, the Bluetooth host module 76 .
[0080] Referring now to FIG. 32 , wireless control unit 130 includes a housing 140 , enclosed at one end by a battery door 142 . Disposed within housing 140 are a plurality of battery contacts 146 and a pair of batteries 148 . Electrical leads 150 connect the batteries to a main printed circuit board 154 which is coupled to a lower, radio frequency (RF) printed circuit board 158 by connectors 160 , 162 (see FIG. 33 b ). A graphic overlay member 166 includes a plurality of dome switches 168 . The dome switches make electrical contact with contacts 170 carried on main printed circuit board 154 , in a conventional manner.
[0081] Referring now to FIGS. 33 a , 33 b an electrical schematic diagram for circuitry carried on printed circuit boards 154 , 158 , is shown. A microprocessor 176 is carried on the lower, RF printed circuit board 154 and has connections coupled to connector 160 . Microprocessor 176 is commercially available as part no. BC219159BN-E4, from CSR located in Cambridge, UK. Microprocessor 176 is connected to an antenna 180 for radio frequency communication with the Bluetooth host module 76 described above. Asynchronous communication with a microprocessor 184 carried on main printed circuit board 154 is made by leads 182 which connect terminals J 10 , J 11 of microprocessor 176 to terminals 8 and 9 of microprocessor 184 via connectors 160 , 162 . Microprocessor 184 is commercially available as part no. PIC16LF627A-041/SS, from Microchip Technology of Chandler, Ariz. Also associated with microprocessor 176 is a crystal-controlled clock circuit 188 and a connector 190 to provide external control programming for the Bluetooth functions of microprocessor 176 .
[0082] A Bluetooth enabler circuit 194 is coupled to terminal 7 of microprocessor 184 to enable its Bluetooth operations. Included in circuit 194 is a microprocessor, part no. MAX4795EUK. In effect, circuit 194 functions as an external electronic switch that provides power to the Bluetooth circuit carried on the lower, RF printed circuit board 158 .
[0083] Referring to the upper right hand corner of FIG. 33 b , the main printed circuit board 154 is provided with three membrane switches, including a filter switch 200 , a volume switch 202 and a mode switch 204 . These switches are connected to terminals 12 , 13 and 14 of microprocessor 184 and provide input control signals. Main printed circuit board 154 is also provided with a plurality of indicator lights arranged in a bank or array 206 . The indicator lights preferably comprise light emitting diodes, although virtually any type of indicator can be used whether visual, audible or vibratory. LED 210 , when illuminated, indicates high volume operation of the detection system, while LED's 212 , 214 indicate a low volume and a volume off operation of the detector system. Indicator light 216 indicates that power to the detector system has been turned off, confirming to the user that the detector system is not emitting signals which might possibly be detected by outside observers. Indicator lights 218 , 220 indicate familiar “city” and “highway” operation (i.e. low gain and high gain operation, respectively) of the detector system. Indicator lights 222 , 224 , are provided for optional functions such as voice control and audible “tones” outputs of the detector system.
[0084] The detector system of the preferred embodiment uses a wireless control link between wireless control unit 130 and Bluetooth host module 76 . In the preferred embodiment, the wireless protocol is chosen to be a Bluetooth protocol although virtually any wireless protocol can be employed, as desired. The wireless control unit 130 is expected to be operated from within the vehicle passenger compartment to provide control over the detector system and to provide an indication of system status to the user. If desired, the wireless link can be replaced with a wired connection. Programming of microprocessor 60 (see FIG. 9 ) and microprocessor 176 (see FIG. 33 a ) preferably includes an algorithm which provides current state recall, defined herein as the current operational mode of the overall detector system. According to one aspect of the present invention, the detector system employs current state recall which not only allows the wireless control unit 130 to consume very small amounts of power and to have an ultra small size, but which also requires a minimum amount of electronics to implement the overall system. For example, the current state recall operation of the detector system, in the preferred embodiment, requires only two micro controllers (microprocessor 184 of FIG. 33 b and microprocessor 64 of FIG. 9 ) and two Bluetooth transceivers (microprocessor 60 of FIG. 9 and microprocessor 176 of FIG. 33 a ).
[0085] Referring to FIG. 33 b , upon the pressing any of the switches 200 , 202 , 204 the respective terminals of microprocessor 184 connected to the switches detects a voltage rise. In response, code associated with microprocessor 184 closes a circuit or switch internal to the microprocessor that outputs a command signal on terminal 7 which in turn is delivered to terminal 3 of the microprocessor of Bluetooth enabler circuit 194 . The Bluetooth enabler circuit 194 responds by applying power to the Bluetooth circuit associated with microprocessor 176 , enabling the microprocessor of the wireless control unit 130 to receive a status signal from host module 76 , via the wireless Bluetooth link. The microprocessor 184 processes the incoming status signal and determines which of the appropriate indicator lights 210 - 224 should be illuminated to indicate visual status of system operation to the user. For example, concerning the current volume mode of the detector system, only one of the indicator lights 210 , 212 and 214 should be illuminated at any one time to indicate only one of the three possible volume operating modes (i.e. volume high, volume low, or volume off). If the incoming status signal received from host module 76 by wireless control unit 130 indicates that system volume is turned off, microprocessor 184 would issue a signal to indicator light 214 to illuminate that indicator light. Similarly, only one of the indicator lights 218 , 220 is expected to be illuminated at a particular time so as indicate to the user that the system is operating in city (low gain) mode or highway (high gain) mode.
[0086] Referring now to FIG. 34 a sequence diagram indicating operation of the overall detector system is shown. In step 240 , a key press or “any—key—down” is sensed by microprocessor 184 . In response, the microprocessor sends a power up signal to the Bluetooth circuitry associated with microprocessor 176 . As mentioned, a “Bluetooth enable” signal is sent to external solid-state switch circuit 194 , through which power is applied to the Bluetooth portion of microprocessor 176 . In step 246 the last state of the overall system is sent to the array of indicator lights. Upon powering up, the Bluetooth circuitry attempts to connect to the host module 76 .
[0087] Upon a successful connection, the host Bluetooth module 76 (see FIG. 9 ) syncs the RF link with the wireless remote 130 and confirms the connection using the standard Bluetooth connection protocols outlined in the Bluetooth standard, as indicated in step 248 . At this time, the host module 76 sends a status signal to the Bluetooth module 176 , using system status information stored in the host module memory. The Bluetooth module of the wireless control unit 130 then communicates to the microprocessor 184 that an RF link has been established between the wireless control unit 130 and host module 76 , (as indicated in step 250 ) and passes the status signal information to microprocessor 184 , updating or confirming the present system status to the wireless control unit 130 . If desired, the indicator lights of the wireless control unit can be cleared upon an initial key press, with reception of the status signal from the host module determining the state of the indicator lights, rather than serving as a data update. At this point, a timed interval is initiated. In the preferred embodiment, the time interval has a 5-second duration, although virtually any duration can be employed. During the time interval each key press of the wireless control unit 130 is passed to the host module 76 as indicated at 254 . Only key presses made during the timed interval, i.e. while the Bluetooth connection is active, are passed to the host module 76 . If there is no key press activity during the time interval, the timer of the wireless control unit 130 expires, and microprocessor 184 triggers Bluetooth enable circuit 194 to open, thus breaking the Bluetooth connection with the host module 76 . The microprocessor 184 then returns to a sleep mode drawing only a minimal amount of current from the small power system, preferably the batteries 148 .
[0088] Referring to FIG. 35 if Bluetooth connection between host 76 and wireless control unit 130 is not established within 5 seconds, the wireless control unit 130 sends a command to Bluetooth enable circuit 194 to open a Bluetooth transmission link and to enter a sleep mode.
[0089] As mentioned, the preferred embodiment employs Bluetooth protocols between the wireless control unit 130 and the host module 76 , to allow the host module to communicate with the wireless control unit as if it were another remote sensor of the system. Although less preferable, other, mixed protocols can be employed, if desired, with different protocols used for the remote sensors and for the wireless remote unit 130 .
[0090] The drawings and the foregoing descriptions are not intended to represent the only forms of the invention in regard to the details of its construction and manner of operation. Changes in form and in the proportion of parts, as well as the substitution of equivalents, are contemplated as circumstances may suggest or render expedient; and although specific terms have been employed, they are intended in a generic and descriptive sense only and not for the purposes of limitation, the scope of the invention being delineated by the following claims.
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A communication system for a vehicle traveling over a road surface is provided with at least one detector for sensing speed detection signals impinging on the vehicle, to monitor the speed of the vehicle or a nearby vehicle. A radiofrequency transmitter communicates the detector output to a receiver adjacent the passenger compartment of the vehicle. The receiver controls one or more annunciators to output one or more annunciator indications to the system user. The radiofrequency transmitter in one embodiment directs transmissions along a ground skip path, reflecting information over the road surface so as to enter the receiver located in or near a passenger compartment of the vehicle. A wireless control unit provides indication of system operating status and allows a user to input commands to the system.
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CROSS REFERENCED TO RELATED APPLICATIONS
This application claims the benefit under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 61/035,480, filed Mar. 11, 2008 and is hereby incorporated by reference in its entirety.
BACKGROUND
Wireless Personal Area Networks (WPAN) communication systems are extensively used for data exchange between devices over short distances of no more than 10 meters. Current WPAN systems exploit the frequency band in the 2-7 GHz frequency band region and achieve throughputs of up to several hundred Mbps (for Ultra-WideBand systems).
The availability of 7 GHz of unlicensed spectrum in the 60 GHz band and the progress in the RF IC semiconductor technologies are pushing the development of the millimeter-Wave (mmWave) WPAN systems which will operate in the 60 GHz band and will achieve the throughputs of about several Gbps. Currently a number of standardization groups (Institute for Electronic and Electrical Engineers (IEEE) 802.15.3c, IEEE 802.11ad, Wireless HD SIG, ECMA TG20) are working on the development of the specifications for such mmWave WPAN networks. The standards are developed mainly as addendums to the previous WPAN standards with the introduction of new PHY layers and also are trying to reuse most of the MAC functionality. However, the modifications to the MAC layer are also required to exploit specific mmWave WPAN characteristics.
A communication link operating at 60 GHz is less robust due to the inherent characteristics of high oxygen absorption and significant attenuation through obstructions. In order to satisfy the link budget requirement, directional antennas have been envisioned to be used in creating a mmWave communication link.
Even if directional antennas are available, for initial device discovery, association and synchronization, the use of omni (or quasi-omni) beacons is typically required. The way a station (STA) performs an omni directional transmission changes according to the antenna type employed, but the bottom line is that regardless of how it is accomplished, the overhead associated with omni transmissions is very high since omni frames are transmitted at very low data rates (few Mbps) as compared to the multi-Gbps data rates that are used for directional transmissions.
Future mmWave WPAN will widely use directional antennas. The high gain of the directional antennas will be required to achieve the necessary signal to noise ratio (SNR) margins over very wide bandwidth (˜2 GHz) mmWave WPAN links under the limited (˜10 dBm) transmitted power. The high-gain antennas may have to be steerable in order to support arbitrary placement of different devices (e.g. to not be limited to fixed positions).
Thus, a strong need exists for new techniques and improvements in millimeter wave wireless technologies.
BRIEF DESCRIPTION OF THE DRAWINGS
The subject matter regarded as the invention is particularly pointed out and distinctly claimed in the concluding portion of the specification. The invention, however, both as to organization and method of operation, together with objects, features, and advantages thereof, may best be understood by reference to the following detailed description when read with the accompanying drawings in which:
FIG. 1 illustrates a Superframe structure wherein a Discovery Beacon (DB) is transmitted during the Beacon Time (BT), while Announcement Beacons/Frames (ABs) are transmitted during the Announcement Time (AT) according to embodiments of the present invention; and
FIG. 2 illustrates a structure of the AB period (AT) according to embodiments of the present invention;
It will be appreciated that for simplicity and clarity of illustration, elements illustrated in the figures have not necessarily been drawn to scale. For example, the dimensions of some of the elements are exaggerated relative to other elements for clarity. Further, where considered appropriate, reference numerals have been repeated among the figures to indicate corresponding or analogous elements.
DETAILED DESCRIPTION
In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the invention. However, it will be understood by those skilled in the art that the present invention may be practiced without these specific details. In other instances, well-known methods, procedures, components and circuits have not been described in detail so as not to obscure the present invention.
Although embodiments of the invention are not limited in this regard, discussions utilizing terms such as, for example, “processing,” “computing,” “calculating,” “determining,” “establishing”, “analyzing”, “checking”, or the like, may refer to operation(s) and/or process(es) of a computer, a computing platform, a computing system, or other electronic computing device, that manipulate and/or transform data represented as physical (e.g., electronic) quantities within the computer's registers and/or memories into other data similarly represented as physical quantities within the computer's registers and/or memories or other information storage medium that may store instructions to perform operations and/or processes.
Although embodiments of the invention are not limited in this regard, the terms “plurality” and “a plurality” as used herein may include, for example, “multiple” or “two or more”. The terms “plurality” or “a plurality” may be used throughout the specification to describe two or more components, devices, elements, units, parameters, or the like. For example, “a plurality of stations” may include two or more stations.
Embodiments of the present invention provide a novel multiple level (such as two-level) beacon mechanism, consisting of low-rate omni discovery beacons and high-rate directional announcement beacons/frames. Discovery beacons may carry only essential information to enable network entry and initialization, and this may include the transmitter (e.g., PNC) ID, timing information, association period signaling, etc. Announcement beacons carry full information required for regular network operations, such as channel scheduling, management and security information, etc.
It is critical that the beaconing mechanism in mmWave systems be designed in such a way to maximize efficiency. To accomplish this, embodiments of the present invention provide that multi-level beacons be used. In particular, for mmWave systems an embodiment of the present may provide a two-level beaconing mechanism comprised of two types of beacons:
Discovery beacon (DB): this beacon is transmitted in (a low-rate) omni mode. It allows new STAs to discover and potentially join the network (i.e., piconet), in addition to serving currently associated STAs. The DB may be a broadcast frame.
Announcement beacon/frames (AB): this beacon/frame is transmitted in (a high-rate) beamformed mode. This frame/beacon may be transmitted by, say, the piconet coordinator (PNC) and targets piconet STAs that are beamformed with the PNC and may be already associated. The AB is a unicast frame addressed to a particular STA and may require the receiving STA to transmit back another frame in response to the reception of the AB frame.
The structure of the superframe 110 is shown generally as 100 of FIG. 1 . The DB is transmitted during the Discovery Time (DT), while the announcement beacons/frames are transmitted during the Announcement Time (AT) 160 . The Data Transfer Time (DTT) 170 is used for the actual data communications amongst STAs which are part of the network, the Association Beamforming Training (A-BFT) 140 is used for beamforming training of a new STA 145 attempting association with the network, and the Beamforming Training Time (BFTT) 175 is for beamforming amongst STAs that are already associated with the network.
Since the DB is less efficient than the AB (since it is transmitted in omni mode), it does not need to be transmitted in every superframe. One of the primary purposes of the DB and AB is synchronization. Hence, a STA must receive either the discovery beacon or announcement beacon/frame to be considered synchronized. If a STA misses a consecutive number of beacons from the PNC, it is considered not synchronized. In this case, the STA shall stop transmissions during the DTT and must restart the piconet joining procedure.
While the DB is sent in omni mode 120 , 180 (Omni/Dir is shown at 130 ) with the intention to be received by all of a PNC's neighbors, the announcement frame/beacon is a high-rate transmitted only to a subset of the beamformed and, most of the time, associated STAs. This allows the PNC flexibility in balancing aspects such as discovery latency and performance. Announcement beacons are also more conducive to better spatial reusability since these beacons are always transmitted in beamformed mode, and provide better efficiency when the number of supported antenna elements is higher than the number of STAs associated with the PNC.
FIG. 2 , shown generally as 200 , illustrates the structure of the AT period 210 where AB frames are exchanged. Each Request frame shown in FIG. 2 is a general name for an AB frame, and could be, for example, replaced by any of the management frames present in IEEE 802.11. The Request frame is a unicast and directed frame addressed to a particular STA and carries, for example and not by way of limitation, the channel time scheduling of the network. For each Request frame, there must be a response from the addressed receiver. This response may be a management frame (e.g., association request, channel time allocation request) or, if there is no management frame to be transmitted, simply an ACK.
Because for each Request there is a Response frame, this allows the PNC 220 and STA 230 to monitor and maintain the beamformed link between them. If the PNC does not receive a response frame after it transmits a request frame to a STA, it may conclude that the link is no longer valid and may reschedule the beamforming between the PNC and the affected STA.
Multiple Request/Response frame exchanges can take place during the AT 210 . Also, Request and Response transmissions between the PNC 220 and a STA 230 may occur more than once over the same AT 210 .
To minimize overhead associated with omni transmissions, information carried in DB is kept to a minimum and may include the PNC ID, timing information, number of beacon transmissions left (in case of directional beacons), etc. In contrast, since it is transmitted in high-rate, the announcement beacon/frame contains all the necessary information required to make the network function, such as channel scheduling, control and management information, piconet synchronization information, etc.
To improve efficiency, DBs may not be present in every superframe. If DBs are used infrequently, then the piconet performance can be substantially improved since less overhead will be paid in using low-rate omni transmissions.
If a PNC wants to serve multiple associated STAs in a superframe, the PNC can transmit multiple announcement frames/beacons during the AT period of that superframe. The announcement beacon contains the superframe time allocation including when the PNC will be ready to receive from and/or transmit to the STA. This allows STAs who receive an announcement frame/beacon to synchronize their schedule with that of the PNC.
Finally, for STAs that are in power save mode, the PNC does not send them announcement beacon/frames.
While certain features of the invention have been illustrated and described herein, many modifications, substitutions, changes, and equivalents may occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.
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According to aspects of the embodiments, there is provided a method and apparatus for communicating in a wireless network with a MAC layer that uses multi-level beacons, the multi-level beacons including a discovery beacon which is transmitted in an omni mode and an announcement beacon/frame transmitted in a beamformed mode.
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APPLICATION DATA
This application claims benefit to U.S. Provisional Application No. 60/206,327 filed May 23, 2000.
FIELD OF INVENTION
The present invention relates to synthesis of heteroarylamine intermediate compounds.
BACKGROUND OF THE INVENTION
Aryl- and heteroaryl-substituted ureas have been described as inhibitors of cytokine production. These inhibitors are described as effective therapeutics in cytokine-mediated diseases, including inflammatory and autoimmune diseases. Examples of such compounds are reported in WO 99/23091 and in WO 98/52558.
A key step in the synthesis of these compounds is the formation of the urea bond. Various methods have been reported to accomplish this. For example, as reported in the above references, an aromatic or heteroaromatic amine, II, may be reacted with an aromatic or heteroaromatic isocyanate III to generate the urea IV (Scheme I)
If not commercially available, one may prepare the isocyanate III by reaction of an aryl or heteroaryl amine Ar 2 NH 2 with phosgene or a phosgene equivalent, such as bis(trichloromethyl) carbonate (triphosgene) (P. Majer and R. S. Randad, J. Org. Chem. 1994, 59, 1937) or trichloromethyl chloroformate (diphosgene) (K. Kurita, T. Matsumura and Y. Iwakura, J. Org. Chem. 1976, 41, 2070) to form the isocyanate III, followed by reaction with Ar 1 NH 2 to provide the urea. Other approaches to forming the urea reported in the chemical literature include reaction of a carbamate with an aryl or heteroaryl amine, (see for example B. Thavonekham, Synthesis, 1997, 1189 and T. Patonay et al., Synthetic Communications, 1996, 26, 4253) as shown in Scheme II below for a phenyl carbamate. U.S. patent application Ser. No. 09/611,109 also discloses a process of making heteroaryl ureas by reacting particular carbamate intermediates with the desired arylamine.
U.S. application Ser. No. 09/505,582 and PCT/US00/03865 describe cytokine inhibiting ureas of formula (I).
An Ar 2 NH 2 required to prepare preferred compounds described therein is illustrated as formula (A).
wherein W, Y, and Z are described below.
The synthesis of II, a preferred formula (A) intermediate was described in U.S. application Ser. No. 09/505,582 and PCT/US00/03865 and is illustrated in Scheme III.
The synthesis begins with a palladium catalyzed carbonylation of 2,5-dibromopyridine (III) to provide ester IV in 55% yield. The reaction is run under pressure (80 psi CO) and must be monitored to minimize formation of the diester, an unwanted by-product. Reduction of IV with diisobutylaluminum hydride at −78° C. provides aldehyde V. This is followed by reductive amination to give VI.
Intermediate VI is then converted to II by reaction with t-BuLi at −78° C. followed by tributyltin chloride to give tributylstannane VII, followed by palladium catalyzed Stille coupling with intermediate VIII to give II. Conversion of VI and analogous intermediates to other intermediates of formula II via Suzuki coupling is also described in U.S. application Ser. No. 09/505,582 and PCT/US00/03865 (Scheme IV). According to this method, intermediate IX is treated with n-BuLi followed by trimethylborate to give arylboronic acid X. Palladium catalyzed Suzuki coupling with VI provides XI, which is deprotected by treatment with acid to give II.
This process is not well-suited for large-scale and commercial use for several reasons. One reaction (Scheme III) is run under high pressure (80 psi) and another at extreme temperature (−78° C.). The yield of IV is only moderate and by-product formation requires a purification step. These factors, plus the cost of starting materials and reagents make this process too costly for commercial scale.
The preparation of 2-bromo-5-lithiopyridine via reaction of 2,5-dibromopyridine with n-BuLi at −100° C. has been described (W. E. Parham and R. M. Piccirilli, J. Org. Chem., 1977, 42, 257). The selective formation of 2-bromo-5-pyridinemagnesium chloride via reaction with 2,5-dibromopyridine with i-PrMgCl at 0° C.—rt has also been reported (F. Trecourt et al., Tetrahedron Lett., 1999, 40, 4339). In these cases, the metal-halogen exchange occurred exclusively at the 5 position of the pyridine ring. However, the syntheses of 5-bromo bromo-2-pyridinemagnesium chloride and 5-chloro-2-pyridinemagnesium chloride have not been reported previously.
The preparation of a lithium intermediate 5-chloro-2-lithiopyridine from 2-bromo-5-chloropyridine, has been reported (U. Lehmann et al., Chem., Euro. J., 1999, 5, 854). However, this synthesis requires reaction with n-BuLi at −78° C. The preparation of the 5-bromo-2-lithiopyridine from 2,5-dibromopyridine was reported by X. Wang et al. ( Tetrahedron Letters, 2000, 4335). However, the method requires cryogenic and high dilution conditions. The selectivity was also dependent on reaction time. It is not suitable for large scale synthesis.
The synthesis of the intermediate 5-bromo-2-iodopyridine by refluxing 2,5-dibromopyridine in HI has been reported (U. Lehmann, ibid). A process using milder conditions for preparing 2-iodopyridine from 2-chloro or 2-bromopyridine has been described (R. C. Corcoran and S. H. Bang, Tetrahedon Lett., 1990, 31, 6757).
SUMMARY OF THE INVENTION
It is an object of the invention to provide novel 2-(5-halopyridyl) and 2-(5-halopyrimidinyl) magnesium halides, novel methods of producing them, and to provide a novel method of using said halides in the efficient synthesis of their respective 5-halo-2-substituted pyridines and pyrimidines.
It also an object of the invention to provide a novel method of producing heteroaryl amines of the formula(A)
wherein Ar, W, Y and Z are described below, the heteroaryl amines are useful in the production of heteroaryl ureas as mentioned above.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
This invention relates to a novel strategy for the synthesis of heteroarylamine compounds of the formula (A) which constitute the key component of pharmaceutically active compounds possessing a heteroaryl urea group.
The invention therefore provides for processes of making a compound of the formula(A)
wherein:
W is CR 3 or N, wherein R 3 is chosen from hydrogen, C 1-5 alkyl, C 1-5 alkoxy, arylC 0-5 alkyl and —COR 4 wherein R 4 is chosen from C 1-5 alkyl, C 1-5 alkoxy, arylC 0-5 alkyl and amino which is optionally independently di-substituted by C 1-5 alkyl, and arylC 0-5 alkyl; W is preferably CH or N,
Ar is chosen from
phenyl, naphthyl, quinolinyl, isoquinolinyl, tetrahydronaphthyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, benzimidazolyl, benzofuranyl, dihydrobenzofuranyl, indolinyl, benzothienyl, dihydrobenzothienyl, indanyl, indenyl and indolyl each being optionally substituted by one or more R 1 or R 2 ;
Y is chosen from
a bond and a C 1-4 saturated or unsaturated branched or unbranched carbon chain optionally partially or fully halogenated, wherein one or more methylene groups are optionally replaced by O, N, or S(O) m and wherein Y is optionally independently substituted with one to two oxo groups, phenyl or one or more C 1-4 alkyl optionally substituted by one or more halogen atoms;
wherein when Y is the carbon chain, the left side terminal atom of Y is a carbon (the atom which is covalently attached to the heterocycle possessing W):
Z is chosen from:
aryl, heteroaryl chosen from pyridinyl, piperazinyl, pyrimidinyl, pyridazinyl, pyrazinyl, imidazolyl, pyrazolyl, triazolyl, furanyl, thienyl and pyranyl and heterocycle chosen from tetrahydropyrimidonyl, cyclohexanonyl, cyclohexanolyl, 2-oxo- or 2-thio-5-aza-bicyclo[2.2.1]heptanyl, pentamethylene sulfidyl, pentamethylene sulfoxidyl, pentamethylene sulfonyl, tetramethylene sulfidyl, tetramethylene sulfoxidyl or tetramethylene sulfonyl, tetrahydropyranyl, tetrahydrofuranyl, 1,3-dioxolanonyl, 1,3-dioxanonyl, 1,4-dioxanyl, morpholinyl, thiomorpholinyl, thiomorpholinyl sulfoxidyl, thiomorpholinyl sulfonyl, piperidinyl, piperidinonyl, pyrrolidinyl and dioxolanyl, each of the aforementioned Z are optionally substituted with one to three halogen, C 1-6 alkyl, C 1-6 alkoxy, C 1-3 alkoxy-C 1-3 alkyl, C 1-6 alkoxycarbonyl, aroyl, C 1-3 acyl, oxo, pyridinyl-C 1-3 alkyl, imidazolyl-C 1-3 alkyl, tetrahydrofuranyl-C 1-3 alkyl, nitrile-C 1-3 alkyl, nitrile, phenyl wherein the phenyl ring is optionally substituted with one to two halogen, C 1-6 alkoxy or mono- or di-(C 1-3 alkyl)amino, C 1-6 alkyl-S(O) m , or phenyl-S(O) m wherein the phenyl ring is optionally substituted with one to two halogen, C 1-6 alkoxy, halogen or mono- or di-(C 1-3 alkyl)amino;
or Z is optionally substituted with one to three amino or amino-C 1-3 alkyl wherein the N atom is optionally independently mono- or di-substituted by aminoC 1-6 alkyl, C 1-3 alkyl, arylC 0-3 alkyl, C 1-5 alkoxyC 1-3 alkyl, C 1-5 alkoxy, aroyl, C 1-3 acyl, C 1-3 alkyl-S(O) m — or arylC 0-3 alkyl-S(O) m — each of the aforementioned alkyl and aryl attached to the amino group is optionally substituted with one to two halogen, C 1-6 alkyl or C 1-6 alkoxy;
or Z is optionally substituted with one to three aryl, heterocycle or heteroaryl as hereinabove described in this paragraph each in turn is optionally substituted by halogen, C 1-6 alkyl or C 0-6 alkoxy;
or Z is nitrile, amino wherein the N atom is optionally independently mono- or di-substituted by C 1-6 alkyl or C 1-3 alkoxyC 1-3 alkyl, C 1-6 alkyl branched or unbranched, C 1-6 alkoxy, nitrileC 1-4 alkyl, C 1-6 alkyl-S(O) m , aryl chosen from phenyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, furanyl, thienyl and pyranyl each aryl being optionally substituted with one to three halogen, C 1-6 alkyl, C 1-6 alkoxy, di-(C 1-3 alkyl)amino, C 1-6 alkyl-S(O) m , or nitrile, and phenyl-S(O) m , wherein the phenyl ring is optionally substituted with one to two halogen, C 1-6 alkoxy or mono- or di-(C 1-3 alkyl)amino;
R 1 and R 2 are independently chosen from: a C 1-6 branched or unbranched alkyl optionally partially or fully halogenated, acetyl, aroyl, C 1-4 branched or unbranched alkoxy, each being optionally partially or fully halogenated, halogen, methoxycarbonyl, C 1-3 alkyl-S(O) m optionally partially or fully halogenated, or phenylsulfonyl;
m= 0, 1 or 2;
All terms as used herein in this specification, unless otherwise stated, shall be understood in their ordinary meaning as known in the art. For example, “C 1-6 alkoxy” is a C 1-6 alkyl with a terminal oxygen, such as methoxy, ethoxy, propoxy, pentoxy and hexoxy. All alkyl, alkenyl and alkynyl groups shall be understood as being branched or unbranched where structurally possible and unless otherwise specified. Other more specific definitions are as follows:
Ac—acetyl;
DBA—dibenzylideneacetone;
DPPF—1,1′-bis(diphenylphosphino)ferrocene;
DPPE—1,2-bis(diphenylphosphino)ethane;
DPPB—1,4-bis(diphenylphosphino)butane;
DPPP—1,3-bis(diphenylphosphino)propane;
BINAP—2,2′-bis(diphenylphosphino)-1,1′-binaphthyl;
DME—ethylene glycol dimethylether;
DMSO—dimethyl sulfoxide;
DMF—N,N-dimethylformamide;
EtO—ethoxide;
i Pr—isopropyl;
t Bu—tertbutyl;
THF—tetrahydrofuran;
RT or rt—room temperature;
The term “aroyl” as used in the present specification shall be understood to mean “benzoyl” or “naphthoyl”.
The term “aryl” as used herein shall be understood to mean aromatic carbocycle, preferably phenyl and naphthyl, or heteroaryl.
The term “heterocycle”, unless otherwise noted, refers to a stable nonaromatic 4-8 membered (but preferably, 5 or 6 membered) monocyclic or nonaromatic 8-11 membered bicyclic heterocycle radical which may be either saturated or unsaturated. Each heterocycle consists of carbon atoms and one or more, preferably from 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur. The heterocycle may be attached by any atom of the cycle, which results in the creation of a stable structure. Unless otherwise stated, heterocycles include but are not limited to, for example oxetanyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothiophenyl, piperidinyl, piperazinyl, morpholinyl, tetrahydropyranyl, dioxanyl, tetramethylene sulfonyl, tetramethylene sulfoxidyl, oxazolinyl, thiazolinyl, imidazolinyl, tertrahydropyridinyl, homopiperidinyl, pyrrolinyl, tetrahydropyrimidinyl, decahydroquinolinyl, decahydroisoquinolinyl, thiomorpholinyl, thiazolidinyl, dihydrooxazinyl, dihydropyranyl, oxocanyl, heptacanyl, thioxanyl, dithianyl or 2-oxa- or 2-thia-5-aza-bicyclo[2.2.1]heptanyl.
The term “heteroaryl”, unless otherwise noted, shall be understood to mean an aromatic 5-8 membered monocyclic or 8-11 membered bicyclic ring containing 1-4 heteroatoms such as N, O and S. Unless otherwise stated, such heteroaryls include: pyridinyl, pyridonyl, quinolinyl, dihydroquinolinyl, tetrahydroquinoyl, isoquinolinyl, tetrahydroisoquinoyl, pyridazinyl, pyrimidinyl, pyrazinyl, benzimidazolyl, benzthiazolyl, benzoxazolyl, benzofuranyl, benzothiophenyl, benzpyrazolyl, dihydrobenzofuranyl, dihydrobenzothiophenyl, benzooxazolonyl, benzo[1,4]oxazin-3-onyl, benzodioxolyl, benzo[1,3]dioxol-2-onyl, tetrahydrobenzopyranyl, indolyl, indolinyl, indolonyl, indolinonyl, phthalimidyl.
Terms which are analogs of the above cyclic moieties such as aryloxy or heteroaryl amine shall be understood to mean an aryl, heteroaryl, heterocycle as defined above attached to it's respective functional group.
As used herein, “nitrogen” and “sulfur” include any oxidized form of nitrogen and sulfur and the quaternized form of any basic nitrogen.
The term “halogen” as used in the present specification shall be understood to mean bromine, chlorine, fluorine or iodine except as otherwise noted. The compounds made by the novel processes of the invention are only those which are contemplated to be ‘chemically stable’ as will be appreciated by those skilled in the art. For example, a compound which would have a ‘dangling valency’, or a ‘carbanion’ are not compounds made by processes contemplated by the invention.
In one embodiment of the invention there is provided a process of making the compounds of formula(A) as described hereinabove,
said process comprising:
a) synthesis of a compound of formula (C) from a compound of formula (B) via substitution with an appropriate halide X c . When X c is Br, methods known in the art may be utilized.
When X c is I, the present invention provides a novel process for the substitution of the leaving group (L) with iodide. This was achieved by using the conditions of R x COCl or (R x CO) 2 O/metal iodide/solvent/heating (25° C.-150° C.), wherein R x is chosen from —C 1-7 alkyl, —CF 1-3 and —CCl 1-3 ; the metal chosen from Na and K, and the solvent chosen from acetonitrile, acetone, DMSO, DMF and THF. Preferred conditions are AcCl and NaI in acetonitrile at 70-90° C. The leaving group L is any suitable leaving group as will be appreciated by those skilled in the art, preferably L is chosen from Cl, Br, —OCOR y and —OS(O) m R y , wherein R y is aryl optionally substituted by C 1-4 alkyl optionally halogenated, such as tolyl, or R y is C 1-4 alkyl optionally halogenated such as CF 3 and CCl 3 , L is more preferably chosen from Br and Cl.
X a is chosen from Br and Cl, preferably Br;
X c is I or Br, preferably I;
X a is attached via the 4 or 5 ring position, preferably the 5 position.
b) In a one pot process, reacting a compound of the formula(C) with a Grignard reagent R—Mg—X b followed by the addition of an E—Y—Z compound wherein Y—Z is as defined above, said E—Y—Z component is further characterized as being an electrophilic derivative of Y—Z and being appropriate for Grignard reagant reactions as will be apparent to the skilled artisan, said reaction taking place in a suitable aprotic solvent at −78° C. to RT, preferably 0° C. to RT for a reaction time of ½ hour to 2 hours, preferably 1 hour, and isolating the compound of the formula (D);
wherein:
X b is chosen from Br, Cl and I;
R is aryl, C 1-6 alkyl or C 5-7 cycloalkyl;
As seen in Scheme V below, this one pot novel process step provides for the formation of the Grignard reagant Compound (F):
where a desirable selective formation was observed. For example the synthesis of 2-(5-halopyridyl)magnesium halides (e.g. 3 and 12) was achieved for the first time.
The process of making compounds of the formula(F) comprises:
reacting a compound of the formula(C)
with a magnesium reagent of the formula R—MgX b ; said reaction taking place in a suitable aprotic solvent at −78° C. to RT, for a reaction time of ½ hour to 2 hours, producing the Grignard compound of the formula(F);
and wherein
X a , is halogen selected from Br and Cl, and X a is attached via the 4 or 5 ring position;
X b is halogen chosen from Br, Cl and I;
X c is I or Br;
W is CR 3 or N, wherein R 3 is chosen from hydrogen, C 1-5 alkyl, C 1-5 alkoxy, arylC 0-5 alkyl and —COR 4 wherein R 4 is chosen from C 1-5 alkyl, C 1-5 alkoxy, arylC 0-5 alkyl and amino which is optionally independently di-substituted by C 1-5 alkyl or arylC 0-5 alkyl; W is preferably CH or N;
preferably CH or N; and
R is aryl, C 1-6 alkyl or C 5-7 cycloalkyl.
In a preferred embodiment there is provided a process for making a compound of the formula(F) as described above and wherein
W is CH;
X a is Br and attached at the 5 ring position;
X c is I;
the temperature is 0° C. to RT; and
the reaction time is 1 hour.
Non-limiting examples of this reaction proceeded with complete selectivity at the 2 position in excellent yield:
In subsequent steps, the novel process of the invention further comprises:
c) reacting the compound of the formula(D) from step b) with an aryl boronic acid of the formula (E), in the presence of a catalyst chosen from nickel and palladium. Regarding the palladium(Pd) catalyst, non-limiting examples are Pd catalysts chosen from Pd(PPh 3 ) 2 Cl 2 , Pd(PPh 3 ) 4 , PdCl 2 (DPPE), PdCl 2 (DPPB), PdCl 2 (DPPP), PdCl 2 (DPPF) and Pd/C; or the combination of a palladium source and an appropriate ligand, with the Pd source, for example, being chosen from PdCl 2 , Pd(OAc) 2 , Pd 2 (DBA) 3 , Pd(DBA) 2 , and with the ligand being chosen from PPh 3 , DPPF, DPPP, DPPE, DPPB, P(o-tolyl) 3 , P(2,4,6-trimethoxyphenyl) 3 , AsPh 3 , P( t Bu) 3 , BINAP, and those bound to solid supports that are mimics of the aforementioned ligands, preferably PdCl 2 and PPh 3 . Regarding the nickel(Ni) catalyst, examples of nickel (Ni) catalyst are those chosen from Ni(PPh 3 ) 2 Cl 2 , Ni(PPh 3 ) 4 , NiCl 2 (DPPE), NiCl 2 (DPPB), NiCl 2 (DPPP), NiCl 2 (DPPF) and Ni/C; or the combination of a Ni source and an appropriate ligand, with the Ni source being NiCl 2 , and with the ligand being chosen from PPh 3 , DPPF, DPPP, DPPE, DPPB, P(o-tolyl) 3 , P(2,4,6-trimethoxyphenyl) 3 , AsPh 3 , P( t Bu) 3 , BINAP, and those bound to solid supports that are mimics of the aforementioned ligands. This reaction takes place in a suitable solvent such as ethylene glycol dimethyl ether (DME), THF, toluene, methylene chloride or water, preferably DME, at 0° C. to 150° C., preferably 25° C. to 100° C., for a period of 1 to 24 hours preferably about 15 hours,
wherein P in the formula(E) is an amino protecting group such as Boc, and subsequently removing said protecting group under suitable conditions to produce a compound of the formula(A).
In a preferred embodiment of the invention there is provided a novel process of making compounds of the formula(A) as described above and wherein:
W is CH;
Ar is chosen from naphthyl, quinolinyl, isoquinolinyl, tetrahydronaphthyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, indanyl, indenyl and indolyl each being optionally substituted by one or more R 1 or R 2 groups;
Y is chosen from:
a bond and
a C 1-4 saturated or unsaturated carbon chain wherein one of the carbon atoms is optionally replaced by O, N, or S(O) m and wherein Y is optionally independently substituted with one to two oxo groups, phenyl or one or more C 1-4 alkyl optionally substituted by one or more halogen atoms; wherein when Y is the carbon chain, the left side terminal atom of Y is a carbon (the atom which is covalently attached to the heterocycle possessing W):
Z is chosen from:
phenyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, imidazolyl, furanyl, thienyl, dihydrothiazolyl, dihydrothiazolyl sulfoxidyl, pyranyl, pyrrolidinyl which are optionally substituted with one to three nitrile, C 1-3 alkyl, C 1-3 alkoxy, amino or mono- or di-(C 1-3 alkyl)amino;
tetrahydropyranyl, tetrahydrofuranyl, 1,3-dioxolanonyl, 1,3-dioxanonyl, 1,4-dioxanyl, morpholinyl, thiomorpholinyl, thiomorpholinyl sulfoxidyl, piperidinyl, piperidinonyl, piperazinyl, tetrahydropyrimidonyl, pentamethylene sulfidyl, pentamethylene sulfoxidyl, pentamethylene sulfonyl, tetramethylene sulfidyl, tetramethylene sulfoxidyl or tetramethylene sulfonyl which are optionally substituted with one to three nitrile, C 1-3 alkyl, C 1-3 alkoxy, amino or mono- or di-(C 1-3 alkyl)amino;
nitrile, C 1-6 alkyl-S(O) m , halogen, C 1-4 alkoxy, amino, mono- or di-(C 1-6 alkyl)amino and di-(C 1-3 alkyl)aminocarbonyl;
In a more preferred embodiment of the invention there is provided a novel process of making compounds of the formula(A) as described immediately above and wherein:
Ar is naphthyl;
Y is chosen from:
a bond and
a C 1-4 saturated carbon chain wherein the left side terminal atom of Y is a carbon (the atom which is covalently attached to the heterocycle possessing W) and one of the other carbon atoms is optionally replaced by O, N or S and wherein Y is optionally independently substituted with an oxo group;
Z is chosen from:
phenyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, imidazolyl, dihydrothiazolyl, dihydrothiazolyl sulfoxide, pyranyl and pyrrolidinyl which are optionally substituted with one to two C 1-2 alkyl or C 1-2 alkoxy;
tetrahydropyranyl, morpholinyl, thiomorpholinyl, thiomorpholinyl sulfoxidyl, piperidinyl, piperidinonyl, piperazinyl and tetrahydropyrimidonyl which are optionally substituted with one to two C 1-2 alkyl or C 1-2 alkoxy; and C 1-3 alkoxy;
In yet a more preferred embodiment of the invention there is provided a novel process of making compounds of the formula(A) as described immediately above and wherein:
Ar is 1-naphthyl wherein the NH 2 is at the 4 position;
Y is chosen from:
a bond, —CH 2 —, —CH 2 CH 2 — and —C(O)—;
In an ultimately preferred embodiment of the invention there is provided a novel process of making compounds of the formula(A) as described immediately above and wherein:
Y is
—CH 2 —;
Z is morpholinyl;
Formation of the reaction intermediate (E) can be accomplished by first protecting an aryl-amine followed by boronic acid formation through a sequence of metal-bromine exchange, quenching with trialkylborate and hydrolysis, as can be seen in Scheme V in the conversion of 7 to 9. Compounds of the formula (E) possessing other desired Ar can be accomplished without undue experimentation by variations apparent to those of ordinary skill in the art in view of the teachings in this specification and the state of the art.
A desirable novel feature of the process of the invention is the selective formation of a 2-(5-halopyridyl) or 2-(5-halopyrimidinyl) magnesium halides, preferably 2-(5-halopyridyl) magnesium halides (e.g. 3 and 12, vide infra), and their subsequent reactions with the in situ generated E—Y—Z electrophiles. Below in Scheme 1, the addition of 2-(5-halopyridyl) magnesium halide 3 to the immonium salt 6 was carried out without the isolation of the immonium salt.
A non-limiting example for a compound of the formula (A) is the amine 1 shown in Scheme V.
Reaction intermediate (2) with a generic formula (B) above can be obtained as exemplified in Scheme VI below. Addition of a copper catalyst may be required for transformations involving certain types of electrophiles, for example the alkylation reaction of the Grignard intermediate with various alkyl halides and epoxides.
Examples of appropriate electrophiles are shown in the table below. Methods of making Y—Z electrophilic derivatives are within the skill in the art. Y component in Y—Z is a derivative of the Y of the formula (A) of the final product upon the addition of the electrophile to the Grignard intermediate. Products may be further derivatized to achieve the desired Y—Z. Such further transformations are within the skills in the art. A non-limiting example is shown below for a preferred embodiment of Z in the formula (A), i.e., the morpholino immonium salt 6. Reference in this regard may be made to Heaney, H.; Papageorgiou, G.; Wilkins, R. F. Tetrahedron 1997, 53, 2941; Sliwa, H.; Blondeau, D. Heterocycles 1981, 16, 2159;.
In this example, E—Y—Z is compound 6, wherein morpholinyl represents Z and Y is —CH 2 — in the final product.
As described above, any electrophile represented by Y, possessing a Z component and compatible with Grignard type reactions are contemplated to be within the scope of the invention. Additional non-limiting examples of E—Y—Z are:
wherein E—Y is an aldehyde such as Z—CHO, thus Y in Formula (A) would be —CH(OH)—.
wherein NRR represent any of the above-listed Z amine moieties or heterocycles possessing a nitrogen heteroatom and Y can be alkylene such as —CH 2 —, X is a countervalent anion.
wherein E—Y is a branched or unbranched alkoxy possessing a halogen atom X and further linked to Z, such as ClCH 2 —O—Z.
wherein E—Y is a C 1-4 acyl halide such as formylchloride, NRR′ represents any of the above-listed Z amine moieties, or heterocycles possessing a nitrogen heteroatom. LG is an appropriate leaving group such as halogens. (see: Katritzky et al., J. Chem. Res. 1999, 3, 230.)
wherein E—Y is a haloester moiety such as chloroformate. X is an appropriate leaving group such as halogens or alkoxy groups. (see: Satyanarayana et al., Synth. Commun. 1990, 20 (21), 3273.)
Z—Y—X 6.
wherein an appropriate Z—Y is substituted by halogen X, preferably iodine, such as CH 3 I.
Addition of an appropriate Z attached to a reactive epoxide provides the hydroxy intermediate which is further derivatized to the desired Y component.
Acylation wherein Y is an acyl attached to Z may be accomplished via the appropriate acylation reagent such as the ester shown above wherein —OR is a known leaving group.
In another embodiment of the invention there is provided a process of making the compounds of formula(A):
wherein Ar and W are as described above;
and wherein for the formula(A):
Y is —CH 2 —; and
Z is chosen from: heterocycle chosen from morpholinyl, thiomorpholinyl, piperidinyl and pyrrolidinyl each of the aforementioned Z are optionally substituted with one to three halogen, C 1-6 alkyl, C 1-6 alkoxy, C 1-3 alkoxy-C 1-3 alkyl, C 1-6 alkoxycarbonyl, aroyl, C 1-3 acyl, oxo, pyridinyl-C 1-3 alkyl, imidazolyl-C 1-3 alkyl, tetrahydrofuranyl-C 1-3 alkyl, nitrile-C 1-3 alkyl, nitrile, phenyl wherein the phenyl ring is optionally substituted with one to two halogen, C 1-6 alkoxy, di-(C 1-3 alkyl)amino, C 1-6 alkyl-S(O) m , or phenyl-S(O) m wherein the phenyl ring is optionally substituted with one to two halogen, C 1-6 alkoxy or di-(C 1-3 alkyl)amino;
or Z is optionally substituted with one to three one to three amino or amino-C 1-3 alkyl wherein the N atom is optionally independently di-substituted by aminoC 1-6 alkyl, C 1-3 alkyl, arylC 0-3 alkyl, C 1-5 alkoxyC 1-3 alkyl, C 1-5 alkoxy, aroyl, C 1-3 acyl, C 1-3 alkyl-S(O) m — or arylC 0-3 alkyl-S(O) m — each of the aforementioned alkyl and aryl attached to the amino group is optionally substituted with one to two halogen, C 1-6 alkyl or C 1-6 alkoxy; or Z is optionally substituted with one to three aryl or heterocycle as hereinabove described in this paragraph each in turn is optionally substituted by halogen, C 1-6 alkyl or C 1-6 alkoxy;
or Z is amino wherein the N atom is optionally independently mono- or di-substituted by C 1-6 alkyl or C 1-3 alkoxyC 1-3 alkyl, C 1-6 alkyl branched or unbranched, C 1-6 alkoxy, nitrileC 1-4 alkyl, C 1-6 alkyl-S(O) m , aryl chosen from phenyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, furanyl, thienyl and pyranyl each aryl being optionally substituted with one to three halogen, C 1-6 alkyl, C 1-6 alkoxy, di-(C 1-3 alkyl)amino, C 1-6 alkyl-S(O) m or nitrile, and phenyl-S(O) m , wherein the phenyl ring is optionally substituted with one to two halogen, C 1-6 alkoxy or mono- or di-(C 1-3 alkyl)amino;
said reaction comprising:
reacting a compound of the formula(C)
with a magnesium reagent of the formula R—MgX b ; said reaction taking place in a suitable aprotic solvent at −78° C. to RT, for a reaction time of ½ hour to 2 hours producing the Grignard compound(F):
wherein
X a , is halogen selected from Br and Cl, and X a is attached to the ring via the 4 or 5 position;
X b is halogen chosen from Br, Cl and I;
X c is I or Br;
W is CH, CCH 3 or N; and
R is aryl, C 1-6 alkyl or C 5-7 cycloalkyl;
subsequently reacting the Grignard compound from the prior step with a N,N-dialkylformamide such as DMF to form an aldehyde:
and isolating the aldehyde;
reacting the aldehyde with an appropriate Z group under nucleophilic addition conditions to provide the compound (D)
This transformation is within the skill in the art and involves reacting of the aldehyde and the appropriate Z component under acidic conditions such as HCl, AcOH, H 2 SO 4 etc, preferably AcOH, in a suitable solvent such as THF, methylene chloride, 1,2-dichloroethane, preferably 1,2-dichloroethane for 0.5-5 h (preferably 2 h) at about RT followed by in situ reduction for 0.5-5 h (preferably 2 h) to provide the product (D).
Subsequent addition of the NH 2 —Ar compound can be done as described hereinabove, to provide the final product compound of the formula(A) as described above in this embodiment of the invention. A non-limiting example of this embodiment of the invention is shown in Scheme VII.
In order that this invention be more fully understood, the following examples are set forth. These examples are for the purpose of illustrating preferred embodiments of this invention, and are not to be construed as limiting the scope of the invention in any way.
SYNTHETIC EXAMPLES
Example 1
Synthesis of 5-bromo-2-iodopyridine from 2,5-dibromopyridine
2,5-Dibromopyridine (100 g) was suspended in acetonitrile (500 mL) at rt. NaI (94 g) and AcCl (45 mL) were added and the reaction was then gently refluxed for 3 h. An aliquot was analyzed by 1 H NMR and MS and the reaction was about 80% complete. The reaction was cooled to rt and quenched with a few mL of water and then K 2 CO 3 aqueous solution to pH 8. EtOAc (1.5 L) was added to extract the organic materials. The organic layer was washed with saturated NaHSO 3 solution, the brine, and then dried over MgSO 4 . Concentration gave crude material that was subjected to the same conditions for about 3 h at which time 1 H NMR showed that the reaction was greater than 97% complete. The same workup provided the crude material. The crude crystals were washed twice with CB 3 CN and dried in the oven. The yield was 95 g.
1 H NMR (CDCl 3 , 400 MHz) δ8.44 (s, 1H), 7.60 (d, J=8.26 Hz, 1H), 7.44 (d, J=8.25 Hz, 1H).
Example 2
Synthesis of 5-bromo-2-formylpyridine from 5-bromo-2-iodopyridine via the Grignard intermediate
In a 22 L 3-neck round bottomed flask equipped with a mechanical stirrer, 1 kg (3.52 mol) of 2-iodo-5-bromopyridine was dissolved in 5 L of THF. The solution was cooled to about −15 to −10° C. 1.9 L (2 M, 380 mol, 1.08 eq) of i PrMgCl was added at a rate to keep the internal temperature below 0° C. The reaction mixture became a brown suspension. After the reaction mixture was stirred between −15 to 0° C. for 1 h, 400 mL (5.16 mol, 1.5 eq) of DMF was added at a rate to keep the internal temperature below 0° C. After stirring at this temperature for 30 min, the cooling bath was removed and the reaction was allowed to warm to room temperature over 1 h. The reaction mixture was then cooled to 0° C. and 4.0 L (7.74 mol, 2.2 eq) of 2 N HCl was added at a rate to keep the internal temperature below 25° C. The mixture was stirred for 30 min, then pH was raised from 1 to a pH 6-7 by adding about 150 mL of 2 N NaOH. The layers were separated and the THF layer was concentrated to give dark brown wet solids. The aqueous layer was extracted with 3 L of CH 2 Cl 2 . The CH 2 Cl 2 layer was used to dissolve the residue obtained from the THF layer, the resulting solution was washed with water (2×2 L), dried by stirring with MgSO 4 (400 g) for 30 min, and filtered. Concentration of the filtrate to dryness gave 583 g of the desired aldehyde as brownish-yellow solids (89% yield after air drying).
1 H NMR (CDCl 3 , 400 MHz) δ10.04 (d, J=0.68 Hz, 1H), 8.86 (t, J=0.52 Hz, 1H), 8.02 (dt, J=8.20, 0.68 Hz, 1H), 7.85 (d, J=8.48 Hz, 1H).
Example 3
Synthesis of 5-bromo-2-(4-morpholinylmethyl)pyridine from 5-bromo-2-iodopyridine via the Grignard intermediate
To a solution of bis(1-morpholinyl)methane (130 mg) in THF (3 mL) at rt was added acetyl chloride (45 mL). The reaction was stirred for 1 h and cooled to 0° C.
In another flask, 5-bromo-2-iodopyridine (130 mg) was dissolved in THF (3 mL) at −40° C. The solution was treated with i PrMgCl (2 M in THF, 0.39 mL) at the same temperature for 15 min. Then the Grignard solution was cannulated into the immonium salt suspension generated above at 0° C. After the addition, the reaction mixture was stirred at rt for 1 h and quenched with saturated NH 4 Cl solution. Extraction with CH 2 Cl 2 , drying over MgSO 4 , filtration and concentration gave a crude oil. This was further purified by column chromatography to afford the product in about 50% yield.
1 H NMR (CDCl 3 , 400 MHz) δ8.60 (s, 1H), 7.76 (d, J=8.24 Hz, 1H), 7.32 (d, J=8.64 Hz, 1H), 3.72 (m, 4H), 3.59 (s, 2H), 2.48 (m, 4H).
Example 4
Synthesis of 5-bromo-2-(4-morpholinyl)methylpyridine from 5-bromo-2-formylpyridine
To a solution of 500 g (2.688 moles) aldehyde in a 5 L of 1,2- dichloroethane at room temperature was added morpholine (1.15 eq, 3.09 moles, 269 ml) in one portion. The reaction temperature went up to 29° C. After stirring the reaction mixture for 15 min, acetic acid (2.1 eq, 5.6 moles, 323 mL) was added in one portion. The temperature rose to 31° C. It was stirred for 1.5 h at room temperature. Sodium triacetoxyborohydride (1.06 eq, 2.85 moles, 604 g ) was added in 100 g portions every 10 min. The temperature was maintained between 35° C. and 46° C. by gentle cooling. It was stirred for an additional 2 h.
The reaction mixture was quenched with 4 N HCl keeping the temperature below 15° C. At the end of addition, the pH of aqueous phase was between 0 and 1 (˜2200 mL). The organic phase was separated and discarded. The aqueous phase was basified with 9 N NaOH (˜740 g NaOH) to pH˜9.5 keeping the internal temperature below 15° C. The product was extracted with methylene chloride. Evaporation of the solvent gave pure amine (660 g, 2.57 moles).
Example 5
Synthesis of 5-Bromo-3-methyl-2-pyridinecarboxaldehyde
An example of the synthesis of a compound of formula (F) in which W is CR 3 (R 3 =methyl), and subsequent reaction with an electrophile is provided below and illustrated in Scheme VIII.
2,5-Dibromo-3-picoline is commercially available or may be prepared from 2-amino-5-bromo-3-methylpyridine by standard diazotization followed by bromination in Br 2 /HBr. Acetyl chloride (0.68 mol, 52.7 mL) was added to a stirring solution of 2,5-dibromo-3-picoline (0.45 mol, 113 g) in acetonitrile (600 mL) followed by sodium iodide (1.66 mol, 250 g) and the reaction mixture was gently refluxed for 18 h. The cooled reaction mixture was filtered and the solid was washed with acetonitrile until colorless. It was suspended in methylene chloride and treated with aq. Na 2 CO 3 until the pH was 10-11. The organic layer was separated, dried over anhydrous sodium sulfate and concentrated to give a brown oil. It was subjected to iodination a second time as above (reflux time 6 h). A dark brown oil was obtained using the same work-up as above. A solution of this oil in hexane was treated with charcoal, filtered and concentrated to give a light brown oil. It slowly solidified on standing to give 5-bromo-2-iodo-3-methylpyridine as a light brown solid (95.0 g, 0.32 mol). Yield: 70%.
2-Iodo-5-bromo-3-methylpyridine (250 mg) was dissolved in THF (4.0 mL). The solution was cooled to 0° C. i PrMgCl (2 M in THF, 0.5 mL) was added at a rate to keep the internal temperature below 5° C. After the reaction mixture was stirred at 0° C. for 1 h, DMF (0.13 mL) was added at 0° C. After stirring at this temperature for 30 min, the cooling bath was removed and the reaction was allowed to warm to room temperature over 1 h. The reaction mixture was hydrolyzed by a saturated aqueous NH 4 Cl solution. Then the aqueous layer was extracted with CH 2 Cl 2 . The CH 2 Cl 2 layer was dried over MgSO 4 and concentrated to give the desired aldehyde as a brownish-yellow solid (80% yield).
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Disclosed are novel 2-(5-halopyridyl) and 2-(5-halopyrimidinyl) magnesium halides, processes of making and their use in the efficient synthesis in their respective 5-halo-2-substituted pyridines and pyrimidines.
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CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation of application Ser. No. 10/819,445, filed Apr. 6, 2004, now U.S. Pat. No. 7,584,577 the contents of which are expressly incorporated herein by reference.
The rain and storm water filtration systems discussed herein relate to filtration systems that employ screens to filter debris and other unwanted material from water streams and, more specifically, to filtration systems having a screen comprising a plurality of wedge wires or tilted wedge wires for filtering water streams.
BACKGROUND
Rainwater downspouts, curbside storm water runoff collectors, and similar water conduits share a common purpose: removal of water from where it is undesired, be it the roof of a building, a city street, a storm basin, or the like. All such conduits allow a volume of water to pass therethrough. Leaf litter, sand, dirt, grit, and other debris cam accumulate within such conduits and clog them, rendering them ineffective. Equally bad, the poor design of many water conduits allows debris to pass through to downstream channels and, ultimately, the ocean, with a consequent negative environmental impact.
Not surprisingly, much effort and money has been spent devising ways to avoid clogged water conduits and contaminated water streams. Patents have been granted for inventions designed to filter water at curbside storm drains (U.S. Pat. No. 6,231,758 to Morris et al.), to treat water in a horizontal passageway (U.S. Pat. No. 6,190,545 to Williamson), to create temporary stream filtration systems (U.S. Pat. No. 4,297,219 to Kirk et al.), to remove downspout debris (U.S. Pat. No. 5,985,158 to Tiderington), and to shield rain gutters on the eaves of a building (U.S. Pat. No. 4,345,925 to Jefferys).
However, with respect to downspouts and storm water systems, the prior art has several shortcomings. Among other things, it is difficult to devise a system that both operates under high flow and effectively filters out small particulate matter and other debris. This is because a filter element that accommodates large flow must also be designed with large spacing to suit the large flow. However, large spacing allows medium to small particulates and waste to pass through unfiltered. Conversely, a filter element designed to trap small particulate matter typically obstructs flow. An ideal water runoff filter would be both capable of passing high flow therethrough and removing small waste and debris.
Accordingly, there remains a need for a filter system for removing debris from a water stream using a filter element that is amenable to high volume flow, capable of removing or trapping waste the size of or even smaller than the size of the gap used for the filter and, preferably, self-cleaning.
SUMMARY
The present invention integrates a Coanda screen (sometimes called “Coanda-effect” screen) into water collection systems such as downspouts, storm runoff collectors, sewer drains, and similar conduits and receptacles. An exemplary embodiment includes retrofitting an existing downspout section (or customizing a new downspout section) with a Coanda screen to provide a downspout with a highly efficient filter for removing debris from a stream of water. Depending on the water flow rate and the size of the debris encountered, different screen sizes and different screen mounting angles may be selected to accommodate the same. Filtered water can pass through the screen, while debris is retained by the Coanda screen and then collected in an optional retaining basket.
In another embodiment, a curbside inlet to a storm drain is fitted with a Coanda screen. The screen is mounted between a raw inlet basin and an outlet basin. Filtered water is allowed to pass over the screen and then fall through the screen into the outlet basin, which then flows onward via an outlet pipe. Captured debris and waste are allowed to fall into a retention basin. To remove waste and debris more effectively, a retaining basket is used. When full, the basket can be lifted out of the curbside inlet and emptied.
In yet another embodiment, there is provided a downspout filter assembly comprising a housing comprising an inlet, and outlet, an interior cavity, and an entrance to the interior cavity; a filter comprising a plurality of wedge wires mounted in the interior cavity of the housing having a portion positioned directly subjacent the inlet; and at least one media pad positioned under the filter for scrubbing water before it exits the outlet.
The present invention may also be practiced by providing a downspout filter assembly comprising a housing comprising an inlet, and outlet, an interior cavity, and at least one surface positioned along a first plane; a Coanda filter positioned inside the interior cavity at an angle to the first plane; one or more media pads positioned in the interior cavity at a position below the Coanda filter.
In still yet another aspect of the present invention, there is provided a downspout filter assembly comprising a housing comprising an inlet, an outlet, and an interior cavity; a pair of rails attached to two sections of the interior cavity; at least one removable container positioned on the pair of rails; a media pad positioned in the at least one removable container or below the at least one removable container; and a filter comprising a plurality of wedge wires mounted in the interior cavity in a position above the media pad.
Yet in another aspect of the present invention, there is provided a downspout filter assembly comprising a housing comprising an inlet, and outlet, an interior cavity, and an entrance to the interior cavity; a filter comprising a plurality of wedge wires mounted in the interior cavity of the housing having a portion positioned subjacent the inlet; and at least one media pad positioned subjacent the filter for scrubbing water before it exits the outlet.
The present invention may also be practiced by incorporating a downspout filter assembly comprising a housing comprising an inlet, and outlet, an interior cavity, and at least one surface positioned along a first plane; a Coanda filter positioned inside the interior cavity at an angle to the first plane; at least one media pad positioned in the interior cavity at a position below the Coanda filter.
Yet, it is also within the spirit and scope of the present invention to incorporate a downspout filter assembly comprising a housing comprising an inlet, an outlet, and an interior cavity; a pair of rails attached to two sections of the interior cavity; at least one removable container positioned on the pair of rails; a media pad positioned in the at least one removable container or below the at least one removable container; and a filter comprising a plurality of wedge wires mounted in the interior cavity in a position above the media pad.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features of the invention will be better understood when considered in conjunction with the accompanying drawings, wherein like part numbers denote like or similar elements and features, and wherein:
FIG. 1 is a side elevation view of a downspout with a Coanda screen in accordance with practice of the present invention;
FIG. 2 is a front elevation view of the downspout of FIG. 1 ;
FIG. 2A is a partial cross-sectional view of a deflector plate;
FIG. 3 is a cross-sectional view of the downspout of FIG. 2 , taken at line 3 - 3 ;
FIG. 4 is an enlarged view of the Coanda screen attached at its downstream end to the downspout;
FIG. 5 is another enlarged view of the same Coanda screen attached at its upstream end to the downspout;
FIG. 6 is an enlarged view of a section of the Coanda screen of FIGS. 4 and 5 ;
FIG. 6A is a depiction of a concave screen surface;
FIG. 7 is a side elevation view of a storm drain system in accordance with practice of the present invention;
FIG. 8 is a top plan view of the storm drain system of FIG. 7 ;
FIG. 9 is a partial cross-sectional view of the storm drain system of FIG. 7 taken at line A-A;
FIG. 10 is a front elevation view of an alternative downspout with a Coanda screen;
FIG. 11 is a side elevation view of the embodiment of FIG. 10 ;
FIG. 12 is a front elevation view of another alternative downspout embodiment with a Coanda screen;
FIG. 13 is a side elevation view of the embodiment of FIG. 12 ;
FIG. 14 is a semi-schematic partial transparent, exploded, and perspective view of an alternative downspout filter assembly provided in accordance with aspects of the present invention comprising a plurality media pads for scrubbing filtered water;
FIG. 15 is a semi-schematic partial transparent, exploded, and perspective view of the alternative downspout filter assembly of FIG. 14 ; and
FIG. 16 is a semi-schematic side view and partial cross-sectional view of the alternative downspout filter assembly of FIG. 14 mounted on a structure and assembled to an upper and a lower downspout section.
DETAILED DESCRIPTION
In accordance with the present invention, a highly effective filter system for a rain water downspout, sewer inlet, curbside storm water drain, or similar water runoff conduit or receptacle is provided. A preferred embodiment of an improved downspout 10 is shown in FIG. 1 . The downspout is mounted to an exterior wall 12 of a building by conventional mounting means (not shown), such as welds, adhesives (e.g., glue, cement, mortar, etc.), mechanical fasteners (e.g., rivets, bolts, screws, clamps, bands, straps. etc.). and other means known in the art. The downspout 10 includes a Coanda screen 20 mounted within a portion 40 of the downspout, referred to herein as an “upgraded downspout portion” or “upgraded downspout section”. The screen is accessible via a downspout opening 60 in the upgraded downspout portion. Water that flows into the downspout from a gutter (not shown) is filtered as it passes through the Coanda screen. Debris caught by the screen can slide out of the downspout opening into an optional retaining basket 80 mounted outside of and below the downspout opening. Effluent from the downspout empties into a splash guard or basin 100 which, preferably, is seated on a concrete slab 102 . Alternatively, the downstream end of the downspout is coupled to an underground header or a drain line (not shown) running to a main sewer or storm drain. The Coanda screen, upgraded downspout portion, retaining basket, and other features are described below in more detail.
An existing downspout can be upgraded or retrofitted by cutting out or otherwise removing a portion thereof, and installing an upgraded downspout portion or section 40 therein, using a slip joint, welds, adhesives, mechanical fasteners, or other conventional attachment means. Alternatively, an entire downspout can be fabricated as such and installed as part of a rain water removal system that includes one or more gutters and mounting hardware. In either case, the improved downspout provides a path for funneling water from a roof (or a deck, mezzanine, or other surface) to grade (e.g., street level) or to a storm water runoff drain or a main sewer line. Effluent from the downspout eventually flows to a storm drain or sewer system and then to the ocean, in some cases via a water treatment facility.
The downspout 10 is preferably constructed of stainless steel, galvanized steel, aluminum, plastic, or some other durable and water-resistant material, and has an interior and an exterior, and a cross-sectional shape that is generally rectangular. Alternatively, the downspout can have a generally circular cross-section or other desired geometry. In an exemplary embodiment, the downspout 10 is physically attached to an exterior wall 12 of a house or a building by any conventional means, such as downspout bands (not shown) anchored to the exterior wall. Water falling into the downspout passes into the upgraded downspout section 40 to the Coanda screen 20 . The Coanda screen 20 allows water to pass through, but traps waste and debris behind.
A Coanda screen acts by a shearing action referred to as the “Coanda effect”, which is discussed below in greater detail. In FIG. 1 , the Coanda screen 20 has an upper surface 22 , a lower or underside surface 24 , a first (upstream) end 26 , a second (downstream) end 28 , and left and right sides, and is made of a plurality of wedge-shaped wires 30 . Additional details of the wires=shape and relative orientation is provided below.
The Coanda screen 20 is mounted at an angle within the upgraded downspout portion 40 , with the upstream end 26 of the screen elevated relative to the downstream end 28 of the screen. As shown in FIG. 1 , the upgraded downspout portion 40 has four walls—front 46 , back 47 , left 48 , and right 49 B and has substantially the same shape and dimensions as the remainder of the downspout. The Coanda screen is affixed within the upgraded downspout portion by e.g., securing the upstream end 26 of the screen to the back wall 47 of the upgraded downspout portion, and the downstream end 28 of the screen to the front wall 46 of the upgraded downspout portion. So installed, the screen is seen to form an angle θ (theta) with the back wall. In practice, it has been found that best results are achieved when θ has a value of about 15 to 50 degrees, more preferably, about 20 to 45 degrees.
To ensure that a substantial portion of the water entering the downspout is filtered, it is preferred that the screen have a large enough area to make contact with all four walls 46 - 49 of the interior of the downspout housing. Alternatively (or, in addition). one or more baffles are mounted within the downspout to divert the flow of water toward the screen. In FIG. 1 , two baffles 52 and 54 are shown secured to the front wall 46 and side wall 48 , respectively, of the upgraded downspout portion at a position above the downspout opening 60 , and oriented such that the baffle projects toward the Coanda screen 20 . The side baffle 54 comprises a front plate 58 and a rear plate 59 . The rear plate 59 is attached to the side wall 48 by known methods, including welding, adhesive, mechanical fasteners and the like while the front plate 58 protrudes from the side wall 48 . The front plate 58 protrusion acts as a diverter to divert water that clings to the side wall towards the screen 20 . Similar attachment and configuration is discussed below for a deflector plate ( FIG. 2A ).
In FIG. 3 , two side baffles 54 and 56 are shown, secured to the left 48 and right 49 side walls of the downspout. Fewer or greater numbers of baffles can be mounted within the downspout to provide optimal diversion of water toward the Coanda screen. For example, the back wall 47 can also be configured to include a baffle. This may be desirable where the upstream end 26 of the screen is not recessed within the surface of the back wall 47 . The presence of such a baffle ensures that water cannot bypass the screen. The baffles can be attached to the inside walls of the downspout using any conventional means, including, without limitation, welding, adhesives, and mechanical fasteners.
The downspout opening 60 provides access to the Coanda screen for maintenance and cleaning. Although the screen is self-cleaning, occasionally debris may become trapped within the downspout or (rarely) wedged between the wires 30 that form the screen. Access to the screen is facilitated by providing the downspout opening 60 with appropriate dimensions relative to the screen 20 . A preferred downspout opening 60 has a width approximately 50-100% of the interior width of the downspout, and a height approximately 33-75% of the vertical profile of the screen 20 , the latter being measured at the wall opposite the downspout opening (the back wall 47 in FIG. 1 ) The downspout opening 60 is located intermediate the upstream and downstream ends of the downspout 10 , but not necessarily equidistant from both ends.
A retaining basket 80 to catch debris caught by the Coanda screen is mounted to the downspout just below a debris deflector plate (further discussed below), using conventional means, such as welding, adhesives, mechanical fasteners, and the like. In an exemplary embodiment, the retaining basket 80 comprises a tightly woven screen made of steel, aluminum, or other weather-resistant material. Debris that does not freely fall into the retaining basket 80 (i.e., debris that clings to the filter due to friction) is eventually pushed out the downspout opening 60 by additional water flowing from the gutter. Water clinging to debris caught in the retaining basket 80 can drip onto the splash guard 100 by passing through the holes of the retaining basket 80 . Alternatively, if an underground header is used to connect with the downspout, water that passes through the retaining basket can be caught by a collector (not shown) mounted beneath the retaining basket, and channeled to the header.
In an exemplary embodiment, the downspout is also equipped with an external debris deflector plate 110 . The debris deflector plate is mounted just below the downspout opening 60 along the external surface of the front wall 46 , just above the retaining basket 80 . The debris deflector plate covers any space between the downspout 10 and the retaining basket 80 , and ensures that debris exiting the downspout opening does not fall between the downspout and the retaining basket.
In an exemplary embodiment shown in FIG. 2A , the deflector plate 110 includes a front plate section 112 configured to deflect debris into the retaining basket, and a rear plate section 114 configured to be attached to the downspout. In an exemplary embodiment, the deflector plate 110 , like the downspout itself, is made of a durable, weather-resistant material, such as aluminum, plastic (e.g., polyvinyl chloride and unplasticized vinyl), galvanized steel, and the like. The deflector plate can be mounted to the downspout by known methods, including welding, adhesives, mechanical fasteners, and so forth.
Reference is now made to FIG. 4 , which is an enlarged view of Detail A indicated in FIG. 1 . The downstream end 28 of the Coanda screen is shown secured to the downspout front wall 46 by an upper bracket 70 and a lower bracket 72 , without obstructing the flow of debris from the upper surface of the Coanda screen into the retaining basket. The two brackets are attached to the downspout by conventional means, such as welding, adhesives, mechanical fasteners, and so forth. Preferably, the upper bracket is substantially flush with the outer wall of the downspout housing at the bottom of the downspout opening.
Similarly, FIG. 5 provides an enlarged view of Detail B indicated in FIG. 1 . The upstream end 26 of the Coanda screen 20 is shown secured to the downspout back wall 47 by upper 74 and lower 76 brackets. However, in addition to securing the upstream end of the screen 20 , the upper bracket 74 also serves to divert water flow along the back wall 47 of the downspout to the screen. Although not shown, similar upper brackets may also be mounted around the entire perimeter of the screen so that any water flow along any of the four downspout walls is diverted toward the screen. The two brackets 74 , 76 are attached to the downspout by conventional means, such as welding adhesives, mechanical fasteners, and so forth.
FIG. 6 shows an exemplary cross-sectional view of the Coanda-effect screen 20 . The screen comprises a plurality of individual wedge wires 30 which are parallel to one another and separated from each other by a gap or spacing 32 . The individual wedge wires 30 are held together in the indicated arrangement by welding two or more backer rods (not shown) to the base portions 34 of each individual wedge wire 30 . Coanda screens are commercially available in several standard sizes. Generally, the difference in screen selection relates the width, height, and tilt angle 36 of the wedge wires, and the gap spacing 32 between the wedge wires. In addition, the Coanda screen may be ordered with an overall concave shape. As shown in FIG. 6A , the term “concave” implies a curved contour when viewed with respect to the upper surface 22 of the screen 20 . When a concave screen is specified, the concave shape has the effect of increasing the tilt angle of the individual wedge wires. This in turn allows the leading (upstream) edge 38 of the wedge wire to shear a greater amount of the water, provided that all other parameters are unchanged. In an exemplary embodiment, the Coanda screen has a gap spacing of about 0.1 to 1.0 mm and a tilt angle of about 3 to 15 degrees, with a radius (“R”) of concavity of from about 6 inches to infinity (when R=infinity, the screen is flat). Alternatively, other screen parameters may be used, taking into account the size of the debris likely to be encountered, the anticipated water flow rate and volume, and so forth.
Coanda screens are available from a number of manufacturers and retailers, including on-line retailers such as www.hydroscreen.com, www.johnsonscreens.com, and www.eni.com/norris/default.html. The screen is described in an article entitled “Hydraulic Performance of Coanda-Effect Screens” by Tony Wahl for publication in the Journal of Hydraulic Engineering, Vol. 127, No. 6, June 2001, the entire contents of which are expressly incorporated herein by reference as if set forth in full.
As explained by Wahl, the Coanda effect is a tendency of a fluid jet to remain attached to a solid flow boundary. As shown in FIG. 6 , when water 130 flows across the screen 20 from the upstream direction, it tends to remain attached to the upper surface of the screen as it travels in the direction of the downgrade 79 . At a given point along the screen, the water has a thickness “X”. As water 130 flows down the screen, its thickness X is sheared by the leading edge 38 of each individual wedge wire 30 . The sheared water is then redirected approximately tangentially 120 to the direction of the original flow due to the contour of the wedge wire 30 . Thus, different wedge wire contour will cause water to be redirected differently. This shearing action is repeated as water traverses down the screen along the direction of the downgrade 79 . Water is sheared as it travels over other wedge wires 30 . After each layer of water is sheared, it is caused to flow along one of several filtered water paths 120 a, 120 b, 120 c, 120 d, etc. The thickness of the water stream gets progressively smaller as the downstream end of the screen is approached, and the flow of water appears to slow to a mere trickle, or even drop off altogether.
This phenomenon is used to great effect in the present invention. Debris-laden water is effectively filtered at the Coanda screen. Any debris that does not fall into the retaining basket 80 during rainfall eventually dries on the screen, and either falls into the basket later, or can be manually removed via the downspout opening 60 .
In an alternate embodiment of the invention shown in FIGS. 7-9 , an effective filter system for removing debris from a storm water runoff collector is provided. The runoff collector 200 comprises a Coanda screen 20 installed between a raw inlet basin 210 and an outlet basin 220 . As before, the screen 20 filters incoming water while trapping debris, but the source of water is a raw stream 212 , from an inlet 214 , and the effluent is a discharge stream 222 for an outlet line 224 .
In an exemplary embodiment, the Coanda screen 20 is mounted between a first weir 230 and a second weir 240 . The screen has a concave surface, with a radius of from about 6 inches to infinity, and is outfitted with an acceleration plate 250 . The acceleration plate 250 is a metal plate of hardened steel, such as stainless steel and the like, mounted to the upstream end 26 of the screen.
The acceleration plate has a width of approximately 2 inches or higher depending on the size of the storm drain system. When water flows from the raw inlet basin 210 over the weir 230 , it has a relatively low flow velocity. If water is allowed to flow over the screen 20 without first having the necessary flow velocity, the screen=s ability to filter out debris will greatly decrease. The acceleration plate provides a vertical drop of about 2 inches or higher, allowing in-coming water to build up velocity before it contacts the first wedge wire on the screen.
Debris caught by the Coanda screen can slide into a retention basket 260 located within a retention basin 262 . In an exemplary embodiment, the retention basket 260 is equipped with a handle 264 , which allows the retaining basket to be lifted out of the basin, whereupon the debris can be discarded. The basket 260 may be a conventional basket and may be constructed out of medium to large steel wire mesh. Due to its size, it may be necessary to lift the basket with a crane or a flit truck having a lift.
In an alternate embodiment of the upgraded downspout 10 shown in FIGS. 10 and 11 , a tapered front wall 46 and a modified back wall 47 having a tapered back wall section 270 is provided. The tapered front wall 46 and tapered back wall section 270 allow the screen 20 to be moved forward in the direction of the retaining basket 80 , and provide clearance for the installation of an acceleration plate 250 . In an exemplary embodiment, additional wall mounted baffles for diverting water toward the screen 20 are not necessary, as the screen is positioned directly below the incoming flow path and even extends past the incoming path. This screen configuration allows all or substantially all of the incoming flow to flow through the screen.
In another alternate embodiment of the upgraded downspout 10 , shown in FIGS. 12 and 13 , an optional hinged cover 272 is provided over the downspout opening 60 of an enlarged upgraded downspout 10 . The enlarged upgraded downspout 10 is slightly larger than a conventional or existing downspout section. but has a much larger depth (the distance between the front wall 46 and the back wall 47 ), e.g., on the order of about 1.3 to 3 times deeper. This allows the enlarged upgraded downspout to accommodate a much larger screen 20 than a standard size upgraded downspout. This in turn, allows the much larger screen 20 to filter substantially all of the incoming flow without the need for wall mounted baffles. However, in the embodiment of FIGS. 10-13 , wall mounted baffles, such as baffles 52 and 54 , can be used.
Referring now to FIG. 14 , a semi-schematic partial perspective-partial transparent view of an alternative downspout filter assembly 280 provided in accordance with aspects of the present invention is shown. In one exemplary embodiment, the downspout filter assembly 280 comprises a housing 282 , having a downspout inlet 284 , a downspout outlet 286 , an interior cavity 288 comprising a plurality of filter components, and an optional door cover 290 . The filter assembly 280 is configured for use in a section of a downspout installed on a structure, such as a parking structure, a building, or other structures that require a water gutter system. As readily apparent, a section of a downspout is to be replaced by the downspout filter assembly 280 . When replaced, an upper or upstream section of the downspout is to be coupled to the downspout inlet 284 by conventional means and a lower or downstream section of the downspout is to be coupled to the downspout outlet 286 also by conventional means. Alternatively. the downspout outlet 286 may be coupled directly to a drain or remain opened to drain over a surface drain. The filter assembly 280 is adaptable in that it may be installed in an existing downspout section or be part of a new downspout installation.
In one exemplary embodiment, the filter components comprise a Coanda filter 20 , a collection container or a debris container 292 , an outlet container 294 , and a filter medium 296 , which may comprise one or more media pads 298 a, 298 b for one or more different filtering functions. Alternatively, a filter comprising a plurality of wedge wires may be used to filter debris and other contaminants, with tilted wedge wires or Coanda screen being more preferred. Screen pith wedge wires are commercially available, for example, through Goel Engineers in India, which has the following website: http://www.goelka.com/wws.htm. The filter components are housed inside the interior cavity 288 of the housing 282 and are closed therein by a door cover 290 abutting the housing flange 300 and a latch 302 , which may embody a key lock or other prior art means for securing the door to the flange. In one exemplary embodiment, the door cover 290 may comprise two or more door sections and may include a gasket 304 for providing a relatively tight seal as compared to when no gasket is used. The gasket may include any prior art gaskets and may adhere to the door cover by adhesive. The door cover 290 is connected to the housing 282 via one or more conventional hinges or fasteners. For venting, one or more vent holes 291 may be incorporated on one or more sides of the housing 282 . If the vent holes 291 are incorporated, they are preferably positioned at a location with minimal water splash.
The housing 282 may comprise a number of different shaped configuration, such as a rectangular shaped box, a square shaped box, or a cylindrical shaped box, with a rectangular shaped box being more preferred. The housing 282 may be made from a number of metallic sheets, such as stainless steel sheets, tin sheets, sheet metal, and zinc coated sheet metal with stainless steel sheets being more preferred. Alternatively, plastic, fiberglass, or synthetic plastic materials may be used.
Referring to the referenced length L, height H, and width W of the housing 282 , in a preferred embodiment, the filter assembly 280 is mounted along a lengthwise direction L against a structure 348 ( FIG. 16 ). To facilitate attachment along the lengthwise direction L, the housing 282 includes a pair of mounting flanges 306 a, 306 b, one along the upper housing section and one along the lower housing section. Alternatively, the filter assembly 280 may be mounted along the width direction W by incorporating the two mounting flanges 306 a, 306 b along the width edge of the upper and lower sections of the housing 282 .
Also shown in FIG. 14 is an optional final treatment filter media 308 . The final filter media 308 , when incorporated, is to be positioned in a sump 310 , which is the space defined by the area under the two containers 292 , 294 and the bottom of the housing 282 . The media pads 298 a, 298 b and the final filter media 308 , when incorporated, are configured to remove organic compounds, toxic metals, particulates, and other undesirable contaminants. The various filter medium may comprise, for examples, e.g., activated carbon, Rubberizer® polymers and particulate products, metal absorbing soy bean hulls, peat, siliceous rocks, activated silica, Miex resins, and potassium permanganate pellets. Depending on the contaminants to be removed, the particular media to be used can be selected accordingly. As an alternative or in addition to the absorbent pads, pelletized hypochlorite or other formulations of chlorine may be used as a media to kill undesirable bacteria, such as E - coli bacteria. Still alternatively, where electricity power is available, the housing may be equipped with UV (ultraviolet) lamps to provide ultraviolet radiation to also kill undesirable bacteria. Conventional mounting means for mounting UV lamps in a wet environment would be required if UV lamps are incorporated.
Broadly speaking regarding operation of the downspout filter assembly 280 , during a rain storm or cleaning operation in which water is used, water is directed down a downspout, flows through the downspout inlet 284 , is filtered by the Coanda filter 20 , in which solids and other suspended contaminants are filtered by the filter 20 and are trapped along the upper surface of the filter and the passes through to the outlet container 294 . The trapped solids and other suspended contaminants are subsequently collected in the collection container 292 , either by being pushed into the container 292 by later trapped solids, gravity, or by a service technician. The filtered water that passes through the filter 20 is additionally filtered by the filter medium 296 positioned in the outlet container 294 and by the final filter media 308 located in the sump 310 , if incorporated. Water then flows out the filter assembly 280 via the downspout outlet 286 .
Referring now to FIG. 15 in addition to FIG. 14 , an exploded perspective view of the downspout filter assembly 280 provided in accordance with aspects of the present invention is shown. The filter 20 incorporated herein is similar to the filter described above with reference to FIGS. 1-6A , and, in addition, may include both wedge wires and tilted wedge wires. A baffle or plate 312 , which may embody a rectangular metallic or plastic plate, is connected to the lower edge of the filter 20 with a second plate 314 connected to the filter 20 at its underside to form an inverted “V” shaped ledge 316 . When assembled, the ledge 316 is adapted to receive or rest on the support rim 318 of the collection container 292 and the support rim 320 of the outlet container 294 (See, e.g., FIG. 14 ) while the upper filter section rests against the back wall of the housing 292 . Optionally, latching mechanisms may be used to removably fasten the filter inside the housing using conventional fastening means.
The containers 292 , 294 incorporated herein may be made of a metallic mesh material for durability, such as a stainless steel mesh material. However, rubber or hard plastic containers may also be incorporated where desired. In one exemplary embodiment, the mesh size for the collection container 292 should be smaller than the mesh size for the outlet container 294 to prevent or minimize small solids collected in the collection container 292 from escaping through the plurality of openings provided by the mesh. Obviously, the mesh size for both containers can be similarly sized for ease of manufacturability. Handles 322 may be added to the containers 292 , 294 for ease of handling the containers during cleaning or other maintenance operation when the containers are removed from the interior cavity 288 .
The outlet container 294 and the media pads 298 a, 298 b should be sized such that the perimeter of the pads contacts the interior surface of the outlet container 294 when the media pads 298 a, 298 b are placed therein ( FIG. 16 ). As readily apparent, this configuration ensures that water entering the outlet container 294 will pass through the media pads 298 a, 298 b before it exists the downspout outlet 286 . The pads 298 a, 298 b are positioned in the outlet container by stacking and resting them directly on the base of the container 294 . Optionally, a treatment pad separator (not shown) may be placed in the container first before the first media pad is added with additional treatment pads to be placed in between a set of media pads. The overall dimensions of the containers 292 , 294 , media pads 298 a, 298 b, and other components of the filter assembly 280 can vary depending on the volume throughput of the particular downspout, which can vary from installation to installation. In a preferred embodiment, the filter assembly 280 and all its components should be sized to handle about 110% to about 125% of the maximum expected flow rate of the particular downspout section.
In one exemplary embodiment, an exit flow deflector 324 comprising a base 326 and two side walls 328 each comprising a rail or a flange 330 are incorporated in the filter assembly 280 . The base 326 preferably has a surface that is sloped about 10-30 degrees from the surface of the flanges 330 for directing flow entering the sump area 310 , as further discussed below. The flow deflector 324 should have a length and a width approximately that of the outlet container 294 . The flow deflector 324 is preferably made from a rigid material, such as a sufficiently gauged metallic sheet or a hard plastic.
In an exemplary embodiment, a main baffle or deflector plate 332 may be incorporated in the filter assembly 280 . As further discussed below, the main baffle 332 , if desired, may be installed subjacent or behind the filter 20 so that as water passes through the filter 20 , it is deflected away from the back side wall 334 of the housing 282 by the main baffle. As readily apparent, this arrangement allows the baffle to direct water away from the housing wall so that the water can then flow through the outlet container 294 where it could be scrubbed or cleaned by the media pads 298 a, 298 b, When installed, the surface of the main baffle 332 should be angled about 5-30 degrees relative to the back sidewall 334 . Rivets, spot welding, brackets, fasteners, or other conventional attachment means may be used to attach the flange section 336 of the main baffle 332 to the back sidewall 334 .
Two brackets or rails 338 , one on an outside sidewall 340 and one on an inside sidewall 342 , are incorporated for placement of the exit flow deflector 324 and the two containers 292 , 294 thereon. The rails 338 , which resemble right-angle brackets, provide two ledges that protrude from the two sidewalls 340 , 342 . The ledges are configured to support the deflector 324 and the two containers 292 , 294 when the same are placed thereon. More particularly, the rails 338 support the deflector 324 and the two containers 292 , 294 by first placing the two flanges 330 of the deflector 324 on the rails 338 and then placing the containers 292 , 294 over the rails, with the outlet container 294 preferably placed directly over the deflector 324 (See. e.g., FIG. 1 ). The sump 310 is an area defined in part by the base of the containers 292 , 294 when over the same are placed on the rails 338 .
A containment dam 342 is positioned at the entrance 344 to the interior cavity 288 of the housing 282 . The containment dam 342 preferably contacts and forms a seal with the two side walls 340 , 342 and the base wall 346 of the housing. The containment dam 342 preferably extends about ⅕ to about ⅓ of the height of the entrance 344 , and should at least be level with or rises above the surface of the rails 338 . The containment dam 342 may be attached to the housing using any prior art methods, including forming the dam by bending a portion of one or more of the sidewalls and then using welding or epoxy to seal the seam.
Referring now to FIG. 16 in addition to FIGS. 14 and 15 , a semi-schematic side view and partial cross-sectional view of the downspout filter assembly 280 is shown mounted on a structure 348 . As previously discussed, the filter assembly 280 may be mounted by fastening the upper and lower mounting flanges 306 a, 306 b to the structure using a plurality of fasteners 350 . The inlet 284 and outlet 286 are strapped or clamped to the upper downspout section 352 and lower downspout section 354 , respectively, using fastening clamps or straps 356 in combination with pliant wrappers 358 . The pliant wrappers can embody rubber sheets or other equivalent materials. However, any prior art coupling means may optionally be used to couple the inlet and outlet of the system 280 to the upper and lower downspout sections.
As shown when water 360 enters the downspout assembly 280 via the inlet 284 and into the interior cavity 288 , the water makes contact with the filter 20 . As previously discussed, debris and other solids carried by the water 360 are then trapped by the filter 20 along the upper surface 22 of the filter. The solids and the debris are then pushed by the stream of incoming water and incoming solids, and/or by gravity, and fall into the collection container 292 . Water, however, passes through the filter 20 to the underside 24 of the filter in the direction of the main deflector plate 332 . During normal flow, water flows in a downward direction towards the outlet container 294 , where it is then cleaned or scrubbed by the media pads 298 a, 298 b before being deflected again by the exit flow deflector 324 . The exit flow deflector 324 channels the water over the final filter media 308 where it is further cleaned or scrubbed before existing the housing 292 via the outlet 286 .
As readily apparent, the media pads 298 a, 298 b, 308 may be eliminated, replaced with other media pads, or used in combination with additional media pads depending on the desired outcome and/or on environmental regulations. When media pads are used, treatment pad separators 362 may be used to separate the media pad from an adjacent pad or from a solid surface, such as the bottom of the housing. The separators 362 may be made from nylon or plastic webbing sheets such as spun-bonded webbing sheets, steel mesh, porous media, or other material to provide gaps or passages for the water flow.
In an exemplary embodiment, a passage 364 is provided internally of the interior cavity 288 for bypassing water 360 around the media pads 298 a, 298 positioned inside the outlet container 294 . This passage 364 is located intermediate the lower edge of the main deflector 332 and the top of the outlet container 294 proximate the back sidewall 334 of the housing 292 . In the event the media pads 298 a, 298 b are clogged and water backs up in the outlet container 294 , water can escape through the passage 364 to then flow out of the housing 292 via the outlet 286 .
Although the invention has been described with reference to preferred and exemplary embodiments, various modifications can be made without departing from the scope of the invention, and all such changes and modifications are intended to be encompassed by the appended claims. For example, an upgraded downspout section can be manufactured as a separate unit and installed as a new downspout. Other materials than those described herein can be used to make the various components of the apparatus described. Changes to the way the baffles are installed, the way they are shaped, the way the deflector plates are installed, and the way the screens are installed within the housing can be made. Other alterations and modifications may be made by those having ordinary skill in the art, without deviating from the true scope of the invention.
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A debris-filtering downspout and other water runoff conduits and receptacles are disclosed, and include a screen mounted within a conduit, a culvert, a storm water conveyance or secured to a water collection basin. The screen provides high water throughput and is self-cleaning while effectively filtering debris contained in an incoming water stream. Optionally, media pads may be included to further scrub the water before it exits the downspout assembly.
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BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a knitted article on a flat knitting machine.
In particular for clothing articles with pockets or collars or with special pattern effects, the parallel production of a base knitted texture and a partial knitted texture is desired. Also, no limitation must be imposed for the utilized formation technique for the basic and partial knitted textures. Known knitting processes could not satisfy these requirements. It is however known to produce pockets by a hose round knitting technique, so that the basic knitted texture with this technique has left stitches in the region of the pocket rear base, which distorts the optical impression of the knitted product since the pockets mainly slightly protrude, so that also the pocket background is seen.
In accordance with another process, the pockets are produced as hose-shaped dents of the base knitted texture, whose side edges are sewn together later, which leads to high manufacturing expenses.
SUMMARY OF THE INVENTION
Accordingly, it is an object of present invention to provide an improved for producing a knitted article on a flat knitting machine.
In keeping with these objects and with others which will become apparent, in order to avoid the above mentioned limitations, a method is proposed for producing a knitted article on a flat knitting machine with two opposite needle beds and a loop transfer device, in which a knitted article has a base knitted texture and at least one parallel partial knitted texture overlapping partially the base knitted texture, and at least in the region of the parallel partial knitted texture or textures at most each second needle of a needle bed is provided with a stitch of the base knitted texture and a knit-provided needle of the needle opposite to one needle bed of the other needle bed is empty, and the stitches of at least one parallel partial knitted texture are produced in the needles which are not provided with the base knitting stitches and the stitches of the base knitted texture in the region of at least one parallel partial knitted texture before the production of stitches for the parallel partial knitted texture are transfer on the other needle bed.
With this method, parallel partial knitted textures can be formed at any point on the base knitted textures. The base knitted texture can have any known structure or color pattern, which can be knitted with the needle division of the inventive method. The formation techniques can vary over the surface of the base knitted texture. The same is true for the parallel partial knitted texture produced with the inventive method. Also, the geometrical shape of the base knitted texture and the parallel partial knitted texture is completely arbitrary. The parallel partial knitted textures can be produced both on the front side and on the rear side of the base knitted texture, and connected at least at one point with the base knitted texture. The connection with the base knitted texture can be performed by tuck loops. Therefore the connections can be produced both along the edges of the parallel partial knitted texture and also with punctual connections.
The inventive method can be varied so that inventive method parallel partial knitted textures can be produced, which have a rib knitted region as well as parallel partial knitted texture which are formed as strip-shaped, plane rib knitted textures which are alternatingly appear on the front and rear side of a base knitted texture. In accordance with a further feature of the present invention, the inventive method can produce a base knitted texture with a parallel knitted texture, a right-right knitted texture with regions of constant knitting width, regions knitting expansion and regions of a knitted width reduction.
The novel features which are considered as characteristic for the present 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 drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is view schematically showing a knitted article with a pocket formed as a parallel partial knitted texture;
FIG. 2 is a view showing a stitch course for producing the knitted article of FIG. 1;
FIG. 3 is a schematic view of a knitted article with a band-shaped parallel partial knitted texture which alternatingly extends on the front side and the rear side of the base knitted texture;
FIG. 4 is a view showing a stitch course for producing the knitted article of FIG. 3;
FIG. 5 is a view schematically showing a knitted article with a reverse collar which is formed as a parallel partial knitted texture;
FIG. 6 is a view showing a stitch course for producing of individual regions of the knitted articles of FIG. 5.
DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 shows a base knitted texture 10, for example a plane right knitted texture, with a pocket 11 provided on its front side and formed also as a plane right knitted texture. The upper edge 11.1 of the pocket 11 is formed as a rib knitted texture. The whole pocket 11 is produced as a parallel partial knitted texture to the base knitted texture 10, and the method which is used is shown in FIG. 2 as to its stitch courses. In row 1 the right stitches of the base knitted textures is formed with needles B, D, F, H, J, L, N, P, R, T in the knitting direction from right to left with a first knitting system S1. Thereafter, in row 2 in the same knitting direction the stitches of the base knitted structure H, J, L, N are dropped in the region of the parallel partial knitted textures of the rear needle bed with the second knitting system S2. In row 3, right stitches are formed with the needle G, I, K, M, O for the parallel partial knitted structure in a carriage direction from right to left with a third knitting system S3. The needle P produces a tuck, whereby the parallel partial knitted structure is connected to the base knitted structure. In row 4, a back hanging of the stitches of the base knitted structures on the needles of the front needle bed is performed.
In the rows 5-8, the same knitting course is performed as in the rows 1-4 in the knitting direction from left to right. The process can be repeated until the desired height of the parallel partial knitted structure, here the pocket 11 is obtained as a plane right knitted structure. In the rows 9-16 the production of the rib knitted edge 11.1 of the pocket 11 is presented. In the row 9 first again a stitch row for the base knitted texture is performed in the knitting direction from right to left with the first knitting system S1. Then the stitches H, J, L, N of the base knitted structure in the region of the parallel partial knitted structure as well as the left stitches I, M of the parallel partial knitted texture are hungover. In row 11, the right and left stitches are parallel partial knitted texture, whereby the rib structure of the edge 11.1 of the pocket 11 is produced. The needle P forms again a tuck loop for binding the pocket 11 on the base knitted texture. In row 12 the stitches of the base knitted texture h, j, l, n as well as the left links of the parallel partial knitted textures i, m are hung back from the rear needle bed H, to the front needle bed V. Subsequently, in the rows 13-16 the same knitting process is performed as in the rows 9-12 in a reverse carriage direction from left to right. The steps of the rows 9-16 are repeated until the rib edge 11.1 of the pocket 11 reaches a desired height.
FIG. 3 shows a knitted article 20 with a special effect pattern which is formed by a smooth left knitted base surface 21 on which a band-shaped parallel partial knitted texture 22 is arranged. Wherein the parallel partial knitted texture extends on a visible side of the plane right knitted texture and alternatingly in the regions 22.1 on the front side of the base knitted texture 21 and in the regions 22.2 on the rear side of the base knitted texture 21. The stitch course shown in FIG. 4 deals with a high register of the base knitted texture 21 with a region 22.1 and a region 22.2 of the band-shaped parallel knitted texture 22. First in row 1, a stitch row for the base knitted texture 21 is formed on the rear needle bed H with a first knitting system S1 in the carriage direction from right to left. Then in row 2 in the same carriage direction a right stitch row for the parallel partial knitted texture 22 is produced with a second knitting system S2. In row 3 a stitch row formation for the base knitted texture in the carriage direction from left to right is performed, before in row 4 again a stitch row for the parallel partial knitted texture is formed on the front needle bed V. The steps of the rows 1-4 are subsequently repeated until the desired height of the region 22.1 of the parallel partial knitted texture 22 is obtained on the front side of the base knitted texture 21.
Then in row 5 all stitches F, H, J, L, N of the parallel partial knitted texture 22 are transfer from the front needle bed V to the rear needle bed H whereby the parallel partial knitted texture 22 alternates on the rear side of the base knitted texture 21. Subsequently in row 6 a stitch row for the base knitted texture 21 is produced on the rear needle bed. Then in row 7 the stitches g, i, k, m of the base knitted texture 21 in the region of the parallel partial knitted texture 22 are transfer from the rear needle bed H to the front needle bed V, and in row 8 with a third knitting system S3 a stitch row is produced for the region 22.2 of the parallel partial knitted texture 22 in the carriage direction from left to right. In row 9, the stitches of the base knitted texture 21 are again transfer from the rear needle bed H and in row 10 a stitch row for the base knitted texture 21 can be produced on the rear needle bed in the carriage direction from right to left. Subsequently the stitches g, i, k, m of the base of the knitted texture 21 are transfer from the rear needle bed H to the front needle bed V, and then a stitch row for the parallel partial knitted texture 22 is produced on the rear needle bed H in row 12. In row 13 again a return hanging of the stitches of the base knitting texture 21 is performed on the rear needle bed H. The steps shown in rows 6-13 can be repeated until the region 22.2 of the parallel partial knitted texture 22 reaches on the rear side of the base knitted texture 21 a desired height. Subsequently the stitches of the parallel partial knitted texture f, h, j, l, n, as shown in row 4, are transfer from the rear needle bed H to the front needle bed V, whereby the parallel partial knitted texture 22 again alternates on the front side of the base knitted texture 21. By the repeated performance of the steps in accordance with FIG. 4, the pattern register of the parallel partial knitted texture can be repeated as often as desired.
FIG. 5 shows a knitted article 30 which is composed of a smooth knitted base knitted texture 31 and a reverse collar 32 produced as a right-right parallel partial knitted texture for the base knitted texture 21. The reverse collar 32 is assembled of regions with a knitted expansion V, regions with a knitted width reduction M and regions with constant knitting width N. In the regions V and M the expansion or width reduction are performed not directly at the left edge but instead substantially offset as shown in a broken line 33. FIG. 6 describes the production of the individual regions N, V and M of the reverse collar 32. In the rows 14 first the production of a region N with a constant knitting width is illustrated by the stitch course. In row 1 a stitch row of the base knitted texture is formed on the front needle bed V in the knitting direction from left to right with the first knitting system S1. Subsequently in row 2, the stitches L, N, P, R, T, V, X, Z of the base knitted texture 31 are formed with the second knitting system S2 in the region of the parallel knitted reverse collar 32 as well as left stitches M, Q, U of the parallel partial knitted texture 32 are transferred from the needle bed V to the rear needle bed H. Therefore in row 3 left and right stitches are formed for the parallel partial knitted structure 32 with the first knitting system S1 in the carriage direction from right to left. The needle Y carries a connection stitch for the base knitting texture 31, or in other words for the stitch of the needle Z. In row 4 the stitches l, n, p, r, t, v, s, z of the base knitted texture 31 and also the left stitches m, q, u are hang back to the front needle bed 8. The steps of the rows 1-4 can be repeated until the region N has the desired length.
The production of a region V with an extension of the parallel partial knitted texture 32 are shown in the rows 5-13. In row 5 a stitch row for the base knitted texture 31 is formed on the front needle bed V from left to right in the carriage direction with the first knitting system S1. Subsequently in the same carriage direction with the knitting system S2, all stitches of the base knitted texture 31 as well as the left stitches M, Q and U of the parallel partial knitted texture 32 are transfer from the front needle bed V to the rear needle bed H in row 6. In row 7 the formation of the right and left stitches for the parallel partial needed texture 32 is performed in the carriage direction from right to left with the knitting system S1. Subsequently in row 8, the right stitches K, O, S, W, Y are transmitted to the rear needle bed H. In row 9, after a needle bed displacement of the rear needle bed H, a part of the stitches of the parallel partial knitted texture k, m, o, q is transfer to the front needle bed 8 with the first knitting system S1 in the carriage direction from left to right. The stitches of the needle K are transferred to the needle I, the stitches of the needle m are transferred to the needle K, the stitches of the needle o are transferred to the stitches M, and the stitches of the needle q are transferred to the needle O, whereby the expansion of the parallel partial knitted texture 32 is produced.
Subsequently the rear needle bed H is displaced back, and in row 10 the left stitches K, O are transfer from the front needle bed V to the rear needle bed H, and the right stitches s, w, y are transfer from the rear needle bed H to the front needle bed V. In row 11 left and right stitches are formed from the parallel partial knitted structures 32 in the carriage direction from left to right with the first knitting system S1. The needle q forms additionally a tuck loop, which provides a marking of the limiting line between the offset stitches and the non offset stitches, see line 33 in FIG. 5. In row 12 in the same knitting direction all stitches which are located on the rear needle bed, or in other words all stitches of the base knitted texture 31 as well as the left stitches k, o, u of the parallel partial knitted texture 32 are transfer to the front needle bed D. In row 13 a stitch row for the base knitted texture 31 is again formed in the carriage direction from right to left with the first knitting system S1. Subsequently the steps of the rows 5-13 can be repeated until the desired expansion of the parallel partial knitted texture 32 is obtained.
The rows 14-22 show the production of a region M of the reverse collar 32 with a reduction of the knitting width. In row 15 a stitch row for the base knitted texture 31 is formed in the knitting direction from left to right with the first knitting system S1 on the front needle bed 8. Subsequently, in the same carriage direction all stitches of the base knitted texture 31 and the link stitches I, M, Q, U of the parallel partial knitted texture 32 are transferred in the same carriage direction with the knitting system S2 in row 15. After this, in row 16, left and right stitches for the parallel partial knitted texture 32 are formed with the first knitting system S1. The needle Y carries the connecting stitches for the base flat knitted texture 31. In row 17 also right stitches G, K are produced from right to left with the knitting system S2 on the left edge of the parallel partial knitted texture 32 from the front needle bed V to the rear needle bed H, and the light stitches q, u are hang over at the right edge of the partial knitted texture 32 from the front needle bed V to the rear needle bed H, and left stitches q, u are transfer on the right edge of the partial knitted texture 32 from the rear needle bed H to the front needle bed V. Then only those stitches g, i, k, m are located on the rear needle bed H, which participate in the subsequent reduction process. For this purpose, the rear needle bed H is displaced, and subsequently in row 18 with the first knitting system S1 in the carriage direction from left to right the stitches of the needle q is transfer to the needle K, the stitch of the needle i is transfer on the needle m and the stitch of the needle k is transfer to the needle o of the front needle bed V. With this hanging over process the reduction of the width of the parallel partial knitted texture 32 is performed. Subsequently in row 19 after a reverse displacement of the rear needle bed H, a hanging over of the left stitches M, Q, U of the parallel partial knitted structure 32 is performed from the front needle bed V to the rear needle bed H, and before in row 20 in the carriage direction from left to right left and right stitches are formed with the first knitting system S1 for the parallel partial knitted texture 32. Subsequently in row 21 all stitches of the rear needle bed H, or in other words, all stitches of the base knitted texture 31 as well as the left stitches m, q, u of the parallel partial knitted texture 32 are transferred to the front needle bed V. Then in row 22 a stitch row is formed on the front needle bed V for the base knitted texture 31. Also, the steps of the rows 14-22 can be repeated until the region M of the parallel partial knitted texture 32 is reduced to the desired width.
The examples of the base knitted textures with parallel partial knitted textures shown in the drawings are however only exemplary. With the inventive method a plurality of further combinations of the base knitted textures and parallel partial knitted textures can be produced.
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 methods differing from the types described above.
While the invention has been illustrated and described as embodied in method for producing a knitted article on a flat knitting machine, 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.
What is claimed as new and desired to be protected by Letters Patent is set forth in the appended claims:
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A method for producing a knitted article on a flat knitting machine with two opposite needle beds and a stitch hanging over device has the steps of providing a knitted article with a base knitted structure and at least one parallel partial knitted texture which partially overlaps the base knitted structure, equipping at least in a region of the parallel partial knitted structure at most each second needle of one needle bed with a stitch of the base knitted texture, emptying a needle of another needle bed which is opposite to the equipped needle of the one needle bed, producing stitches of at least one parallel partial knitted texture in needles which are not equipped with base knitting stitches, hanging over stitches of the base knitted texture in a region of at least one parallel partial knitted texture before producing of stitches for the parallel partial knitted texture on the other needle bed.
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FIELD OF THE INVENTION
[0001] The present disclosure generally relates to footwear accessories and, more particularly, to footwear accessories positionable in footwear to improve wearability.
BACKGROUND
[0002] Finding footwear that fits ideally is oftentimes a difficult task. Additionally, overtime, footwear stretches, deforms, or wears out, thereby providing a poor fit with the user's foot. Footwear can be too large, too small, too wide, too narrow, etc. Unfortunately, such drawbacks are not discovered until the footwear has been worn for a period of time, after which the footwear cannot be returned. Thus, purchasers of the footwear are stuck wearing poorly fitting footwear or they cast aside, discard, or otherwise stop wearing the footwear, thereby resulting in sore feet and/or a waste of money.
SUMMARY
[0003] The present disclosure is defined by the following claims, and nothing in this section should be taken as a limitation on those claims.
[0004] A need exists for a manner of altering inadequately fitting footwear to be more comfortable and adequately fit a wearer's foot.
[0005] In one aspect, a kit is provided and includes a deformable material adapted to be positioned into footwear, and a tool including a first end and a second end. The first end of the tool is adapted to engage the deformable material, move the material to a desired position in the footwear, and shape the material. The second end of the tool is adapted to engage the material and remove the material from the footwear.
[0006] In another aspect, a method of improving wearabilty of footwear is provided and includes positioning a deformable material into footwear, engaging the material with a first end of a tool, moving the material to a desired portion of the footwear with the tool, and deforming the material into a desired shape with the first end of the tool.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The disclosure can be better understood with reference to the following drawings and description. The components in the figures are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the disclosure.
[0008] FIG. 1 is a top front perspective view of exemplary footwear, exemplary material positionable in the footwear, and an exemplary tool for inserting, shaping, and removing the material.
[0009] FIG. 2 is a top view of the footwear and material shown in FIG. 1 with a top portion of the footwear removed to expose the interior of the footwear, the material is shown in a toe portion of the footwear.
[0010] FIG. 3 is a top view similar to FIG. 2 with the material positioned in the shoe and in the process of being moved into the toe portion of the footwear with the tool.
[0011] FIG. 4 is a top view similar to FIG. 2 with the material moved into the toe portion of the footwear and shaped with the tool.
[0012] FIG. 5 is a top view similar to FIG. 2 with the material in the toe portion of the footwear, and the tool positioned in the footwear and engaging the material for removal of the material from the footwear.
[0013] FIG. 6 is a top view similar to FIG. 2 with the material engaged by the tool and in the process of being removed from the footwear.
[0014] FIG. 7 a top view similar to FIG. 2 with the material shown in an arch portion of the footwear.
[0015] FIG. 8 is a top view similar to FIG. 2 with the material shown in a heel portion of the footwear.
DETAILED DESCRIPTION
[0016] With reference to FIG. 1 , an exemplary substance or material 20 is illustrated and is adapted to be positioned in footwear 24 to improve wearability of the footwear 24 . The material 20 is adapted to be positioned in any type of footwear 24 such as, for example, military shoes or boots, stilettos, other high-heel shoes, men's dress shoes, athletic shoes, or any other men's or women's shoe, or any other type of footwear. The illustrated footwear 24 is merely an exemplary type of footwear and is not intended to be limiting. Rather, as expressed above, the material 20 may be positioned in any type of footwear and all of such possibilities are intended to be within the spirit and scope of the present disclosure.
[0017] Footwear oftentimes does not provide desirable wearability to an individual wearing the footwear. For example, the footwear may be inappropriately sized (e.g., too large) to a wearer's foot, thereby causing discomfort to the individual. Also, for example, footwear may have locations causing undesirable discomfort or friction to a user's foot. Moreover, for example, footwear begins to wear or become misshaped overtime and the material 20 is adapted to maintain shape and integrity of the footwear. The material 20 is positionable within footwear to alleviate these undesirable attributes, thereby ultimately improving wearability of the footwear.
[0018] The material 20 includes a variety of characteristics that make it beneficial for improving wearability of the footwear 24 . For example, the material 20 may be malleable, pliable, moldable or otherwise deformable to allow the material 20 to take a desired shape and to provide a relatively soft surface for a user's foot to engage. At the same time, the material 20 is also, for example, sufficiently durable to provide necessary support to the user's foot when in the footwear 24 , inhibit premature deterioration of the material 20 , and facilitate reuse of the material 20 . Moreover, for example, the material 20 may have tackiness or a sufficient level of friction to inhibit the material 20 from slipping within the footwear 24 and/or to inhibit a user's foot from slipping against the material 20 . The material 20 is adapted to remain intact, maintain its molded shape, and remain in position within the footwear 24 when exposed to normal conditions such as, for example, natural foot moisture and normal range of body temperatures. Furthermore, the material 20 may be non-toxic, non-staining, scented or unscented, and may come in a variety of different colors. The various colors may be purely aesthetic and cater to users' color preferences, or the colors may correspond to characteristics of the material 20 such as, for example, durability, tackiness, scent or unscented, size, type of footwear with which to use the material (e.g., men's shoe, women's shoe, athletic shoe, etc.) or any other characteristic of the material 20 to provide a user with visual indication of the characteristics of the material 20 .
[0019] With reference to FIGS. 1 and 2 , the material 20 is positioned in a toe portion 28 of the footwear 24 . If an individual has a shoe that is too large for their foot, the individual may position the material 20 in the toe portion 28 to occupy some of the excess space between the toe of the shoe and the individual's foot. The individual's toes engage the material 20 to provide a better fit and inhibit substantial sliding of the individual's foot within the shoe.
[0020] Referring now to FIGS. 1 , 3 , and 4 , the material 20 may be inserted into the footwear 24 , moved into a desired position within the footwear 24 , desirably shaped, and removed from the footwear 24 using an exemplary tool 32 . The tool 32 may have a variety of different configurations, shapes, sizes, etc. and be within the intended spirit and scope of the present disclosure. Additionally, the tool 32 may be comprised of a variety of different materials such as, for example, plastic, metal, or any other material, all of which are intended to be within the spirit and scope of the present disclosure. Furthermore, the tool 32 may be a one-piece unitarily formed tool or may be comprised of multiple components coupled together in any manner such as, for example, fasteners, welding, bonding, adhering, snap-fit, interference-fit, or any other manner of coupling components together.
[0021] In the illustrated exemplary embodiment, the tool 32 includes a first end 36 adapted to insert, position, and shape the material 20 and a second end 40 adapted to remove the material 20 from footwear 24 . The first end 36 includes an engagement surface 44 adapted to engage the material 20 to move and shape the material 20 . In the illustrated exemplary embodiment, the engagement surface 44 is arcuate and may have a variety of different arcuate sizes and shapes in order to provide a variety of different shapes to the material 20 . In other exemplary embodiments, the engagement surface 44 may have other shapes such as, for example, flat, polygonal, or any other shape, and all of such shapes are intended to be within the spirit and scope of the present disclosure. The engagement surface 44 of the tool 32 engages and is pushed against the material 20 to move the material 20 into the desired portion of the footwear 24 (e.g., the toe portion 28 as illustrated in FIGS. 1-4 ). Then, the material 20 is shaped by further pressing the engagement surface 44 of the tool 32 against the material 20 when the material 20 is in the desired portion of the shoe (as shown in FIG. 4 ). Once the material 20 is desirably shaped, the tool 32 is removed from the footwear 24 and an individual may wear the footwear 24 .
[0022] With reference to FIGS. 5 and 6 , the second end 40 of the tool 32 is adapted to remove the material 20 from the footwear 24 . The second end 40 includes a removal member 48 adapted to engage (see FIG. 5 ) and pull (see FIG. 6 ) the material 20 from the footwear 24 . In the illustrated exemplary embodiment, the removal member is a hook 48 . In other exemplary embodiments, the removal member 48 may be any shape and size as long as it can engage and remove the material 20 from the footwear 24 . The hook 48 is adequately shaped to facilitate penetration of the hook 48 into the material 20 and ensure gripping of the material 20 when the tool 32 is being pulled/removed from the footwear 24 .
[0023] It should be understood that the material 20 may be positioned and desirably shaped anywhere within footwear 24 to improve wearability of the footwear 24 . FIGS. 1-6 illustrate the material 20 positioned and shaped in the toe portion 28 of the shoe. Alternatively, for example, the material 20 may be positioned and shaped in an arch portion 52 (see FIG. 7 ), a heel portion 56 (see FIG. 8 ), or any other location within the footwear 24 . The tool 32 is adapted to insert, position, and shape the material 20 at any location within the footwear 24 . Additionally, the tool 32 is adapted to remove the material 20 from any location within the footwear 24 .
[0024] The material 20 and the tool 32 in combination provide a kit or system 60 adapted to improve the wearability of footwear 24 . The kit or system 60 may be used in variety of different manners, methods, or processes. One exemplary process includes inserting the material 20 into footwear 24 , engaging the material 20 with the first end 36 (e.g., the engagement surface 44 ) of the tool 32 , moving the material 20 into a desired portion of the footwear 24 with the tool 32 , pressing the first end 36 against the material 20 with the material 20 in the desired portion of the footwear 24 to desirably shape the material 20 , disengaging the first end 36 of the tool 32 from the material 20 once the material 20 has the desired shape, and removing the tool 32 from the footwear 24 . The process may further include removal of the material 20 from the footwear 24 by, for example, inserting the tool 32 into the footwear 24 , engaging the material 20 with the second end 40 (e.g., the removal member 48 ) of the tool 32 , penetrating the second end 40 of the tool 32 into the material 20 , withdrawing the tool 32 from the footwear 24 while maintaining engagement between the tool 32 and the material 20 to remove the material 20 from the desired portion of the footwear 24 , and removing the tool 32 and the material 20 from the footwear 24 .
[0025] It should be understood that this exemplary process is only one of many possible manners, methods, and processes of using the kit or system, and this and any of the other possible manners, methods, and processes may include fewer, more, or other steps and be within the intended spirit and scope of the present disclosure.
[0026] The Abstract of the Disclosure is provided to allow the reader to quickly ascertain the nature of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. In addition, in the foregoing Detailed Description, it can be seen that various features are grouped together in various embodiments for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed embodiments require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive subject matter lies in less than all features of a single disclosed embodiment. Thus, the following claims are hereby incorporated into the Detailed Description, with each claim standing on its own as a separately claimed subject matter.
[0027] While various embodiments of the invention have been described, it will be apparent to those of ordinary skill in the art that other embodiments and implementations are possible within the scope of the invention. Accordingly, the invention is not to be restricted except in light of the attached claims and their equivalents.
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Kits, systems, methods, materials, and tools for improving footwear wearability are provided. In one aspect, a kit includes a deformable material adapted to be positioned into footwear, and a tool including a first end and a second end. The first end of the tool is adapted to engage the deformable material, move the material to a desired position in the footwear, and shape the material. The second end of the tool is adapted to engage the material and remove the material from the footwear. In another aspect, a method of improving wearabilty of footwear includes positioning a deformable material into footwear, engaging the material with a first end of a tool, moving the material to a desired portion of the footwear with the tool, and deforming the material into a desired shape with the first end of the tool.
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BACKGROUND OF THE INVENTION
The present invention relates to an edge connector, and more particularly to an edge connector which utilizes a preload cap in order to spread out the contact portions of the terminals prior to mating with an edge card.
Conventionally, an edge connector is used as a direct type connector in which an edge, of a substrate such as a printed circuit board is directly inserted and fitted into connector, as a plug portion as shown in Japanese Patent Application Laid-Open (Kokai) No. H4-126383.
FIG. 14 is a perspective view of sudl a conventional edge connector.
As illustrated in FIG. 14 , the connector has a housing 801 made of an insulating material and includes a plurality of conductive terminals 802 that are held in the housing 801 . Contact portions 803 of the terminals 802 project downward from a lower surface of the housing 801 . 810 designates a substrate such as a printed circuit board or the like having a plurality of pads 811 arranged along and where “t” designates the thickness of the substrate 810 .
In this case, an angled hole 804 is formed in the center portion of the housing 801 , and the hole 804 extends in the direction of the terminals 802 and passes through the housing 801 in the thickness direction. A spacer 805 with a thickness “w” larger than the thickness “t” of the substrate 810 is inserted from above into the angled hole 804 , and the tip of the spacer 805 projects from the lower surface of the housing 801 between the contact portions 803 of the terminals 802 on both sides. The opposing contact portions 803 are forcibly spread by the tip of the spacer 805 , and the distance between the opposing contact portions 803 is equal to or greater than “w”, which is greater than the thickness “t” of the substrate 810 .
As illustrated, the substrate 810 is inserted between the contact portions 803 so that the state in which the contact portions 803 are forcibly spread by the spacer 805 . In this case, the distance between the opposing contact portions 803 is larger than the thickness “t” of the substrate 810 , the contact portions 803 may not buckle or deformed due to the contact by the inserted substrate 810 . The spacer 805 is pushed up by the substrate 810 and the contact portions 803 become deformed so that the distance between them is reduced by the spring force of the contact portions 803 and sandwich the substrate 810 from both sides. Thus, the edge connector is fixed to the substrate 810 . In addition, the contact portions 803 are pressed against the connecting electrodes 811 by the spring force that the contact portions 803 have and are reliably electrically connected thereto.
SUMMARY OF THE INVENTION
However, in the above-described conventional edge connector, since the contact portions 803 of the terminals 802 are held in the state of being forcibly spread by the spacer 805 , it is difficult to apply a preload pressure to the contact portions 803 in advance. In other words, since the spacer 805 has thickness “w” which is greater than the substrate thickness “t”, the distance between the contact portions 803 becomes larger than the thickness “t” of the substrate 810 . For this reason, for instance, when the edge connector is stored in inventory the contact portions 803 are held for a long time and are forcibly spread, a creep or elastic deformation occurs and the contact portions 803 may not be able to return to the original shape, resulting in not being able to sandwich the substrate 810 from both sides with a sufficient force. As a result, the electrical connection between the contact portions 803 and the substrate 810 is more likely to become uncertain.
Furthermore, in the case of inserting the substrate 810 , since the contact portions 803 do not contact the connecting electrodes 811 until the spacer 805 is released from between the contact portions 803 , the wiping effect occurring when the contact portions 803 contact the moving connecting electrodes 811 , that is, the effect of removing the dust, foreign matters, or the like of the connecting electrodes 811 by rubbing them by the contact portions 803 may not be exerted. As a result, the connection between the contact portions 803 and the pods 811 of the substrate 810 becomes uncertain.
An object of the present invention is to solve the above-described problem and to provide an edge connector with a removably attached preload cap for holding terminals such that the distance between the contact portions of the opposing terminals are set to be slightly narrower than the thickness of the substrate to be inserted, thereby the preload given to the terminals may be maintained at an appropriate level, and a creep deformation may not occur in the terminals even when the edge connector is left to stand for a long period of time, whereby the terminals may fully exert their force, sandwich and hold the contact electrodes of the substrate, insertion work of the substrate may be easily performed because the resistance received from the terminals during the insertion work is decreased, a deformation and damage to the terminals may not occur, the electrical connection state of the contact portions of the terminals and the contact electrodes are favorable due to the wiping effect, and with high durability.
For solving this object, an edge connector of the present invention comprises a connector body for engaging with a counterpart connector; terminals extending from the connector body, the terminals including contact portions for contacting electrodes disposed on surfaces of a substrate; the connector body including a mounting part for attaching a removable preload cap; the contact portions being arranged in opposing rows where a distance between the opposing contact portions in an initial state is smaller than a thickness of the substrate, the distance in a state where the preload cap is attached being larger than that of the initial state and smaller than the thickness of the substrate.
In a further aspect of the present invention, the contact portion includes an engaging portion at a tip thereof the preload cap includes a terminal holding portion and the engaging portion is engaged with the terminal holding portion in the state in which the preload cap is attached.
In a still further aspect of the present invention, the preload cap comprises a first preload cap corresponding to one of the rows of the contact portions and a second preload cap corresponding to the other row of the contact portions and the first preload cap and the second preload cap have an identical structure to each other, and are attached to the connector housing so that they face each other.
In a still further aspect of the present invention, an amount of extension of the preload cap attached to the connector body from the connector body is longer than an amount of extension of the contact portion from the connector body.
In the connector according to still further aspect of the present invention, the cap mounting part has a concave portion formed in the connector body outside the mutually opposing rows of the contact portions and the preload cap further includes a fitting projection that is inserted in the cap mounting part.
In the connector according to still further aspect of the present invention, the preload cap forms a substrate insertion opening into which the substrate can be inserted in the state in which the preload cap is attached to the connector body, and the preload cap can then be removed from the connector often when the substrate is inserted in the substrate insertion opening and the distance between the opposing contact portions is spread by insertion of the substrate.
According to the present invention the preload cap for holding the terminals is removably attached so that the distance between the contact portions of the terminals is slightly narrower than the thickness of the inserted substrate. The preload given to the terminals may be maintained at an appropriate level, and creep deformation will not occur in the terminals even when the edge connector is left to stand for a long period of time. Hence, the terminals will fully exert their force and hold the contact electrodes of the substrate and the work of inserting the substrate is easily performed because the resistance received from the terminals during insertion is decreased, and deformation and damage to the terminals does not occur. The connection state of the contact portions and the contact electrodes is favorable due to the wiping effect, and the durability is improved.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a first perspective view illustrating an edge connector according to an embodiment of the present invention in a state in which the edge connector is mounted on a substrate;
FIG. 2 is the same view as FIG. 1 , but illustrating the edge connector mounted to the substrate;
FIG. 3 is a similar view to FIG. 2 ;
FIG. 4 is a cross-sectional view taken along line x-x of FIG. 2 , and illustrating the edge connector is mounted on the substrate;
FIG. 5 is a cross-sectional exploded view illustrating the edge connector before the preload cap is attached thereto;
FIG. 6 is the same view as FIG. 5 , but illustrating the edge connector after the preload cap is attached thereto;
FIG. 7 is a perspective view illustrating the edge connector in with the preload caps attached thereto;
FIG. 8 is the same view as FIG. 7 , but illustrating the edge connector with the substrate is inserted into the preload cap;
FIG. 9 is a cross-sectional view taken along line Y-Y of FIG. 8 , illustrating the edge connector with the substrate is inserted and the preload caps attached thereto;
FIG. 10 is a perspective view illustrating the edge connector with the preload caps removed therefrom;
FIG. 11 is a first perspective view illustrating a counterpart connector of the edge connectors of the present invention;
FIG. 12 is a second perspective view illustrating the opposing end of the counterpart connector of FIG. 11 , to the embodiment of the present invention;
FIG. 13 is a cross-sectional view illustrating the edge connector of the present invention mated to the counterpart connector; and
FIG. 14 is a perspective view illustrating a conventional edge connector.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference numeral 1 designates an edge connector of the present invention, in which an edge portion of a substrate 101 is inserted therein. The substrate 101 is a printed circuit board used in an electronic device such as a computer, or the like, or a flat cable referred to as a flexible printed circuit (FPC), a flexible flat cable (FPC), or the like. In this embodiment, the present invention is explained in terms of the substrate 101 being a printed circuit board. The substrate 101 has a plurality of connecting electrodes or pods 151 arranged at a predetermined pitch on opposite surfaces thereof along the upper edge portion. The pods 151 are connected to conductive traces (not shown) of the substrate 101 . The pitch and the number of the connecting electrodes 151 can be appropriately set.
The connector 1 includes a housing 11 serving as a connector body and made of an insulating material. A plurality of terminals 51 made of conductive metal are fitted in the housing 11 . The housing 11 is an elongated member extending along the edge portion of the substrate 101 and having a rectangular cross-section. It includes a fitting portion 12 integrally formed therewith so as to extend on the opposite side (upper side in the Figure) of the substrate 101 . The fitting portion 12 is a portion that mates to a counterpart or mating connector 201 , and includes a concave portion 13 in which a convex portion 212 of the mating connector 201 is fitted. The concave portion 13 is an elongated groove-like portion having a rectangular cross-section which is open in the surface opposite to the substrate 101 .
The terminals 51 are arranged along the inner wall surface of the concave portion 13 . As illustrated in FIG. 4 , terminal receiving grooves 16 extend through the housing 11 and the portion 12 with, each terminal 51 being accommodated in a single terminal receiving groove 16 . The pitch and the number of the terminal receiving grooves 16 may be changed according to the pitch and the number of the contact pods 151 of the substrate 101 . The terminals 51 need not necessarily be fitted in all of the terminal receiving grooves 16 and the terminals 51 can be omitted according to the arrangement of the contact pods 151 of the substrate 101 .
For the sake of illustration, FIGS. 1-3 illustrate only some of the terminals 51 and contact pods 151 which are positioned on both sides of the substrate 101 in the widthwise direction.
The housing 11 includes flange parts 14 integrally formed therewith that extend outward from both ends of the housing 11 on one side of the substrate 101 (lower side in the Figure) and in the longitudinal direction of the housing 11 , as well as guide parts 15 integrally formed therewith and arranged at the end surface of the housing 11 on the side of the substrate 101 in the vicinity of the ends in the longitudinal direction and extend toward the substrate 101 . The guide parts 15 are members that define the positional relationship between the ends of the substrate 101 (right and left ends in FIGS. 1-3 ) and the housing 11 , and contact both ends of the substrate 101 . In addition, each guide parts 15 includes a first extension portion 15 a and a second extension portion 15 b integrally formed therewith so as to extend in the longitudinal direction of the housing 11 . As illustrated in FIGS. 2-3 , the extent of the first extension portion 15 a is larger than the amount of extension of the second extension portion 15 b . However, the extents of the first extension portion 15 a and the second extension portion 15 b may be appropriately changed. The first extension portion 15 a and the second extension portion 15 b contact opposite surfaces of the edge of the substrate 101 near the ends thereof and define the positional relationship of the substrate 101 in its thickness direction. The guide parts 15 guide both ends of the substrate 101 in the width direction and thickness directions relative to the housing 11 .
The housing 11 includes a cap mounting part 17 formed in the end surface on the side of the substrate 101 and extending longitudinally. The cap mounting part 17 is a groove-like concave portion formed outside the terminal receiving groove 16 , and a fitting projection 22 of the preload cap 21 , (described later) is inserted in the cap mounting part 17 .
As illustrated in FIG. 4 , the terminal 51 has a contact portion 52 integrally connected to the lower end of the terminal body, which extends linearly in the vertical direction and is fixed to the terminal receiving groove 16 . It includes a counterpart contact portion 53 integrally connected to the upper end of the terminal body and contacts a counterpart terminal 254 of a mating connector 201 in the fitting concave portion 13 . The contact portions 52 are arranged in mutually opposing rows as they are in the mating connector contact portions 53 .
The counterpart contact portion 53 includes an inclined portion 53 a and a convex portion 53 b . The inclined portion 53 a extends obliquely upward from the upper end of the terminal body toward the center of the housing 11 in the thickness direction. In addition, the convex portion 53 b is connected to the tip of the inclined portion 53 a and contacts the counterpart terminal 254 of the counterpart connector 201 . When the counterpart connector 201 is fitted in the connector 1 , the distance between the convex portions 53 b on both sides are forcibly spread, and the convex portions 53 b press the mating terminals 254 by an urging force generated due to resilient deformation mainly of the inclined portion 53 a and the connection portion of the terminal body and the inclined portion 53 a.
The contact portion 52 has, as a whole, a mountain shape or a shape with a central peak and gentle slopes, with a first inclined portion 52 a , a convex portion 52 b , a second inclined portion 52 c , and an engaging portion 52 d . The first inclined portion 52 a extends obliquely downward from the lower end of the body toward the center of the housing 11 in the thickness direction. The second inclined portion 52 c is connected to the tip of the first inclined portion 52 a and inclined in a reverse direction to that of the first inclined portion 52 a . The convex portion 52 b is a connecting portion of the first inclined portion 52 a and the second inclined portion 52 c , and in the illustrated embodiment, it is a portion bent approximately at 90 degrees and contacting the connecting electrode 151 of the substrate 101 . In addition, the engaging portion 52 d is connected to the tip of the second inclined portion 52 c , extends nearly parallel to the terminal body in the initial state, and engages with a terminal holding portion 24 of the preload cap 21 .
As illustrated in the Figures, the distance between the opposing convex portions 52 b of the terminals are forcibly spread in the state in which the connector 1 is mounted on the substrate 101 , and the convex portions 52 b presses the connecting electrodes 151 by the urging force generated due to the resilient deformation mainly of the first inclined portions 52 a and the connection portions of the terminal bodies and the first inclined portions 52 a . Thereby, the connecting state of the terminals 51 to the connecting electrodes 151 is reliably maintained. In addition, the state in which the connector 1 is mounted on the substrate 101 is maintained when the substrate 101 is sandwiched by the opposing contact portions 52 . In addition, the terminals 51 and the connecting electrodes 151 can be secured by a securing means such as soldering, or the like. In this case, the electrical connecting state of the terminals 51 to the connecting electrodes 151 can be reliably maintained and the mounting state of the connector 1 on the substrate 101 can be more reliably maintained.
Next, the structure of the preload cap 21 will be explained.
As illustrated in FIGS. 5 , 7 & 8 , a first preload cap 21 A and a second preload cap 21 B are mounted on the connector 1 . The first preload cap 21 A and the second preload cap 21 B have an identical structure, and members belonging to the first preload cap 21 A are allocated a designation of “the first” and appended with the letter “A”, and members belonging to the second preload cap 21 B are allocated a designation of “the second” and appended with the letter “B” for differentiation. It is to be noted that when explanation is made without differentiating the members belonging to the first preload cap 21 A from those of the second preload cap 21 B, the designation of “the first” and “the second” and the letters “A” and “B” will be omitted.
The preload cap 21 A and the preload cap 21 B include elongated rectangular bodies extending longitudinally of the housing 11 , and first end wall portions 23 A and second end wall portions 23 B extending perpendicularly to the bodies are connected to opposite longitudinal ends of the bodies. As illustrated in FIG. 6 , the first preload cap 21 A and the second preload cap 21 B form a rectangular tube having an elongated rectangular cross-section extending longitudinally along the housing 11 . The first preload cap 21 A and the second preload cap 21 B are arranged to face each other. When the first preload cap 21 A and the second preload cap 21 B are mounted on the connector 1 , the bodies which form a pair of elongated side walls cover the outside of the contact portions 52 of the terminals 51 . The end wall portions 23 form a pair of short side walls and cover the outside of the guide parts 15 on opposite ends. An elongated rectangular substrate insertion opening 26 is formed between the first preload cap 21 A and the second preload cap 21 B. Inclined surfaces 27 for guiding the end of the substrate 101 into the substrate insertion opening 26 are formed on the inside ends of the end wall portions 23 on the opposite side of the connector 1 (left side of FIGS. 5-6 ).
The length of the preload cap 21 is longer than the amount of extension of the contact portion 52 of the terminal 51 from the end surface of the housing 11 so that the terminal contact portion 52 are protected by the preload cap 21 and are not be damaged by the contact with fingers of an operator, tools, other peripheral devices, or the like.
In addition, the preload cap 21 includes a fitting projection 22 integrally formed therewith so that it projects from the end surface of the body on the side of the connector 1 toward the connector 1 and extends longitudinally of the body. The preload cap 21 is attached to the housing 11 of the connector 1 when the fitting projection 22 is inserted in the cap mounting part 17 of the housing 11 .
The preload cap 21 also includes a terminal holding portion 24 integrally formed therewith that projects from the inner end of the body on the opposite side of the connector 1 and extends longitudinally of the body. The terminal holding portion 24 has a terminal insertion hole 25 formed therein which extends through the terminal holding portion 24 . When the preload cap 21 is attached to the connector 1 , the engaging portions 52 d of the contact portions 52 of the terminals 51 are inserted in the terminal insertion hole 25 and secured by the terminal holding portion 24 . The amount of extension of the terminal holding portion 24 toward the center in the thickness direction is set such that the distance between the convex portions 52 of the contact portions 52 on opposite sides becomes a value T 2 which is slightly greater than a value T 1 in the initial state as illustrated in FIG. 5 .
The distance between the first terminal holding portion 24 A and the second terminal holding portion 24 B is set to be greater than the value tx of thickness of the substrate 101 , which will be described later. Thereby, since the size of the substrate insertion opening 26 in the thickness direction becomes greater than the value tx of the thickness of the substrate 101 , the substrate 101 can be easily inserted therein.
The first preload cap 21 A and the second preload cap 21 B can be separately and sequentially attached to the connector 1 , as illustrated in FIG. 5 . An operator relatively moves the first preload cap 21 A toward the connector 1 , as indicated by arrow P 1 of FIG. 5 . The operator may insert the first fitting projection 22 A in the upper cap mounting part 17 of the housing 11 , and insert the engaging portions 52 d of the upper terminals 51 into the first terminal insertion hole 25 A so that the engaging portions 52 d engage with the first terminal holding portion 24 A. Subsequently, the operator holds the second preload cap 21 B with hands or fingers and moves it toward the connector 1 , as indicated by the arrow P 2 . The operator may then insert the second fitting projection 22 B in the lower cap mounting part 17 of the housing 11 , and insert the engaging portions 52 d of the lower terminals 51 into the second terminal insertion hole 25 B so that the engaging portions 52 d engage the second terminal holding portion 24 B.
As illustrated in FIG. 6 , the preload cap 21 is attached to the connector 1 . The engaging portions 52 d are engaged with the terminal holding portion 24 and the opposing convex portions 52 b are spread so that the distance therebetween becomes the value T 2 which is slightly greater than the value T 1 in the initial state. The opposing engaging portions 52 d sandwich the first terminal holding portion 24 A and the second terminal holding portion 24 B by an urging force generated due to a resilient deformation of the first inclined portions 52 a and the connection portions of the terminal bodies and the first inclined portions 52 a . Accordingly, the attachment of the preload cap 21 to the connector 1 is reliably maintained by the urging force generated by the terminals 51 .
In addition, when viewed from the side of the terminals 51 , a load that can resiliently deform mainly the first inclined portions 52 a and the connection portions of the terminal bodies and the first inclined portions 52 a is given to the terminals 51 as a pre-load pressure, that is, a preload when the engaging portions 52 d are engaged with the terminal holding portion 24 . In this case, the distance T 2 between the opposing convex portions 52 b is set to be smaller than the value tx of the thickness of the substrate 101 . Therefore, since the amount of deformation of the terminals 51 is small in the state when the preload cap 21 is attached and the preload is given to the terminal 51 , a creep deformation will not occur in the terminals 51 even when the connector is left to stand for a long period of time. Accordingly, as described above, a creep deformation may not occur in the terminals 51 and the terminals 51 can maintain a sufficient elastic force even when the connector 1 is stored for a long period of time in the state in which the preload cap 21 is attached thereto.
The operator relatively moves the substrate 101 and inserts the edge portion of the substrate 101 on the side in which the contact pods 151 of the substrate 101 are disposed into the rectangular tube having the elongated rectangular cross-section formed by the first second preload caps 21 A 21 B facing each other. In FIG. 7 , a rectangular cutaway portion 111 is formed in one end of the edge portion of the substrate 101 . The cutaway portion 111 abuts against the edge of the guide part 15 of the housing 11 and defines the length of insertion of the substrate 101 in between the terminals 51 . It is to be noted that the cut-away portion 111 may be formed in both ends of the edge portion of the substrate 101 , or may be omitted.
In this case, since the both ends of the edge portion of the substrate 101 are guided by the inclined surfaces 27 formed in the end wall portions 23 of the preload cap 21 , the edge portion of the substrate 101 can be easily inserted. When the substrate 101 is further moved into the connector 1 , both ends of the edge portion of the substrate 101 will be guided by the first extension portion 15 a and the second extension portion 15 b of the guide part 15 of the housing 11 . Thus the positional relationship relative to the housing 11 in the width and thickness directions of the substrate 101 are defined, and the connecting electrodes 151 exposed to opposite surfaces of the edge portion of the substrate 101 are reliably set at the position facing the contact portions 52 of the corresponding terminals 51 .
When the substrate 101 is completed by inserted as shown in FIG. 9 , it enters between the terminal contact portions 52 and forcibly spreads the convex portions 52 b of the contact portions 52 apart. When the engaging portion 52 d is engaged by the terminal holding portion 24 , the distance T 2 of the convex portions 52 b on opposite sides is smaller than the value tx of thickness of the substrate 101 , the distance between the convex portions 52 b is forcibly spread by the substrate 101 , and the engaging portions 52 d are in the state of being separated from the terminal holding portions 24 .
In addition, since the size of the substrate insertion opening 26 in the thickness direction is set to be greater than the value tx of the thickness of the substrate 101 , the substrate 101 can be inserted therein without contacting the terminal holding portion 24 .
The substrate 101 enters between the opposing contact portions 52 when the distance between the convex portions 52 b of the contact portions 52 at T 2 (which is greater than T 1 in the initial state) that is, in the state in which preload is given to the terminals 51 , the resistance incurred by the substrate 101 from the terminals 51 decreases as compared to that when the substrate 101 enters between the contact portions 52 in the initial state. The insertion of the substrate 101 is easily performed. The resistance received by the substrate 101 from the terminals 51 is small and the substrate 101 will not be damaged. Likewise the reaction force received by the terminals 51 from the substrate 101 is small and the terminals 51 may will not be deformed or be damaged.
The contact pods 151 move relative to the convex portions 52 b when the convex portions are pressed against the contact pods 151 by an urging force generated due to the resilient deformation of the terminals 51 when the substrate 101 enters between the contact portions 52 . The wiping effect is generated when the convex portions 52 b contact the moving contact pods 151 in the state of being pressed and dust, foreign matters, or the like, is removed by being rubbed by the convex portion 52 b . Likewise, the dust, foreign matters, or the like of the convex portion 52 b may be removed when being rubbed by the contact pods 151 .
The convex portions 52 b press the pods 151 by an urging force and the electrical connecting state of the terminals 51 and the pods 151 is reliably maintained. Creep deformation will not occur in the terminal 51 and since the terminals 51 maintain a sufficient elastic force, the urging force is large enough. Accordingly, the terminal convex portions 52 b press the contact pods electrodes 151 with a sufficiently large force and the contact portions 52 on opposite sides sandwich the substrate 101 with a sufficiently large force.
Subsequently, the operator removes the preload cap 21 from the connector 1 . The operator removes the first preload cap 21 A from the connector 1 , as indicated by the arrow P 3 , and further relatively removes the second preload cap 21 B from to the connector 1 , as indicated by the arrow P 4 . Since the distance between the convex portions 52 b is then spread and the engaging portions 52 d are separated from the terminal holding portions 24 , the urging force generated by the terminals 51 does not act on the preload cap 21 , and therefore the preload cap 21 is freely movable. The preload cap 21 is then easily removed from the connector 1 . ( FIG. 10 )
In the case of securing the terminals 51 and the connecting electrodes 151 by soldering, a solder layer is formed in the surface of the contact pods 151 in advance. The preload cap 21 is removed from the connector 1 and the solder is reflowed by accommodating the connector 1 and substrate 101 in a furnace. Thereby, the connecting state of the terminals 51 and the substrate 101 to the contract pods 151 is reliably maintained.
The counterpart connector 201 includes a counterpart housing 211 made of an insulating material and a plurality of conductive terminals 254 which are fitted in the counterpart housing 211 . The counterpart housing 211 is also an elongated member and as illustrated in FIG. 12 , a fitting opening 214 is formed in the fitting surface and includes a convex portion 212 disposed in the opening 214 . As illustrated in FIG. 13 , the fitting portion 12 of the connector 1 is fitted in the opening 214 and the convex portion 212 is fitted in the fitting portion 12 when the connector 1 and the counterpart connector 201 are mated together.
The counterpart housing 211 includes wire insertion openings 213 that open to the surface on the opposite side of the fitting surface (upper surface in FIG. 11 ). Tips of wires 251 such as coaxial cables, or the like, are accommodated in these openings 213 . The wire terminals 253 are connected to the tips of the wires 251 and the terminals 253 are engaged in the insertion openings 213 . The wire terminals 253 are connected to the corresponding counterpart terminals 254 , and thus, each of the wires 251 is connected to a counterpart terminal 254 .
When the connector 1 and the counterpart connector 201 are mated together, the convex portion 212 enters between the contact portions 53 on the opposite sides. The distance between the convex portions 53 b on the opposite sides is spread apart and the convex portions 53 b press the counterpart terminals 254 by the urging force generated due to a resilient deformation of the inclined portions 53 a and the connection portions of the connector bodies. The connection of the terminals 51 and counterpart terminals 254 is reliably maintained. When the counterpart contact portions on the opposite sides sandwich the convex portions 212 , the mating state of the connector 1 and the counterpart connector 201 is reliably maintained.
In addition, the wires 251 such as coaxial cables, or the like, are not necessarily be connected to the counterpart connector 201 , and for instance, a flat cable such as an FPC, an FFC, or the like, may be connected thereto.
The housing 11 of the connector 1 includes a cap mounting part 17 for attaching the preload cap 21 and the contact portions of the terminals 51 are arranged in opposing rows, and the distance between the opposing contact portions 52 in the initial state is smaller than the thickness of the substrate 101 , while the distance in a state in which the preload cap 21 is attached is larger than that in the initial state and smaller than the thickness of the substrate 101 .
The preload given to the terminals 51 may be maintained to an appropriate amount so that creep deformation will not occur in the terminals 51 even when the connector is left to stand for a long period of time, such as in inventory. Accordingly, the terminals 51 will always a force sufficient to sandwich the substrate 101 . The resistance received by the substrate 101 during an insertion is reduced and the insertion is easily performed, and a deformation or damage may not occur in the terminals 51 . Further, the electrical connecting state of the contact portions 52 of the terminals 51 and the connecting electrodes 151 becomes favorable due to the wiping effect.
In addition, the contact portion 52 includes the engaging portion 52 d at the tip thereof, the preload cap 21 includes the terminal holding portion 24 , and the engaging portion 52 d is engaged with the terminal holding portion 24 in the state in which the preload cap 21 is attached. Thereby, a preload is given to the terminals 51 and the terminals 51 can resiliently and elastically deform. In addition fitting of the preload cap 21 to the connector 1 may be reliably maintained by the urging force generated by the terminals 51 .
The preload cap 21 includes the first preload cap 21 A and the second preload cap 21 B, both of which are preferably identical to each other and are attached to the housing 11 so they face each other. Accordingly, the structure of the preload cap 21 is simplified and the preload cap 21 may be manufactured at a low cost. The first preload cap 21 A and the second preload cap 21 B form what may be considered as a tube for covering the outside of the opposing rows of the contact portions 52 . The length of the preload cap 21 away from the housing 11 is greater than the length the terminal contact portions 52 external from the housing 11 . Thus the contact portions 52 of the terminals 51 are protected by the preload cap 21 and are not be damaged by contact with fingers of an operator, tools or the like.
The preload cap 21 forms the substrate insertion opening 26 into which the substrate 101 can be inserted in the state in which the preload cap 21 is attached to the housing 11 , and the preload cap 21 can be removed from the housing 11 when the substrate 101 is inserted in the substrate insertion opening 26 and the distance between the opposing contact portions 52 is spread by the insertion of the substrate 101 . Thereby, the insertion work of the substrate 101 and the fitting operation of the preload cap 21 may be easily performed.
The present invention is not limited to the above-described embodiments, and may be changed in various ways based on the gist of the present invention, and these changes are not eliminated from the scope of the present invention.
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A circuit board edge connector includes an insulative housing and two opposing mating ends with a plurality of conductive terminals supported by the housing and extending between the two ends. One end of the connector mates with an opposing connector and the other end has a slot disposed therein that receives the mating edge of a printed circuit card or board. The terminals at the end of the connector extend outwardly in a cantilevered fashion and they terminate in free ends that contact conductive pads on the edge of the circuit card. A preload cap is provided that includes two parts that interfit with each other and with the circuit card mating end of the connector. These preload caps engage the terminal free ends and impart a preload to the terminals so that the circuit card may be easily inserted into the connector slot and the caps are subsequently removed from the connector.
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This is a continuation-in-part of copending U.S. Ser. No. 292,864, filed Jan. 3, 1989, now abandoned.
FIELD OF THE INVENTION
This invention relates to a process for production of polyester multi-filament drawn yarn of 2.5 denier per filament or greater, whereby high birefringence (Δn) yarns are prepared at lower spinning speeds and lower intrinsic viscosity than prior art processes.
DESCRIPTION OF THE PRIOR ART
Polyethylene terephthalate filaments of high strength are well known in the art and are commonly utilized in industrial applications including tire cord for rubber reinforcement, conveyor belts, seat belts, V-belts and hosing.
Dimensionally stable polyester (DSP) industrial yarns are desired to minimize sidewall indentations (SWI) in the bodies of radial tires and to achieve good tire handling characteristics. An additional objective is to make advanced DSP's having the strength and modulus equivalent to rayon at elevated tire service temperatures, while using up to 30 percent less material. While the current polyester tire cords have sufficient strength, their elevated temperature modulus is too low. U.S. Pat. No. 4,101,525 to Davis et al. provides a high strength multifilament polyester yarn with low shrinkage and work-loss characteristics. While yarns exhibiting the features taught by Davis are classified as DSP's, they do not meet the modulus requirements for rayon replacement. Additionally, low denier per filament (dpf of 2 or less) and rapid cooling of the filament immediately after emerging from the spinneret can result in excessive filament breakage and thus yield yarn with poor mechanical quality. U.S. Pat. No. 4,491,657 to Saito et al. discloses high modulus, low shrinkage polyester yarn, but requires a low terminal modulus to achieve good yarn to treated cord conversion efficiency for such dimensionally stable yarns. The low terminal modulus is translated into the treated cord and results in a lower tenacity than the high terminal modulus cords made by present invention. The process of Saito et al. requires high spinning speeds, which makes it difficult to incorporate the Saito process into a continuous spin-draw process, whereas the present invention permits the use of lower spinning speeds whereby more readily available and/or less costly equipment can be used.
U.S. Pat. No. 4,690,866 to Kumakowa et al. describes a means of making yarns which yield highly dimensionally stable treated cords using ultra high viscosity polymer. On a comparative experimental basis, i.e. utilizing our solvent system, the Kumakowa intrinsic viscosity (IV) values would be 5% higher than indicated in their patent, i.e. they require a minimum of 0.95 IV polymer by our measurements. Also, these cords have low terminal modulus and hence do not achieve the full tenacity benefit of a given polymer viscosity.
It is known, shown by the prior art cited above, that undrawn birefringence can be increased by increasing the spinning speed or yarn IV.
An important need exists for a process to produce high undrawn birefringence (Δn u ) yarns at lower spinning speeds and lower intrinsic viscosity (IV), than previously. Processing at lower speeds is important because of the speed limitations of commercial equipment, particularly winders. The ability to use lower IV means that costly processing steps such as solid state polymerization or costly/environmentally hazardous additives can be eliminated.
SUMMARY OF THE INVENTION
A process for production of a dimensionally stable drawn polyethylene terephthalate multifilament yarn having filaments of at least 2.5 denier per filament comprising the steps of:
a) extruding a polyethylene terephthalate polymer melt through a spinneret having a plurality of extrusion orifices to form filaments;
b) advancing the extruded multifilament yarn first through a delay zone then through a quenching zone to solidify the filaments in a controlled manner;
c) withdrawing the solidified multifilament yarn from the quenching zone at a desired spinning speed V;
whereby steps a) through c) are performed under conditions to form a partially-oriented multifilament yarn having an undrawn birefringence (Δn u ) of at least 0.020 and wherein Δn u =R f V 2 .0 IV 2 .4 where IV is the intrinsic viscosity of the undrawn yarn and is at least 0.80 and R f is at least 9.0×10 -3 ; then
d) hot drawing the partially-oriented multifilament yarn. The process permits production of high undrawn birefringence yarns at lower speeds and lower IV's than previously demonstrated in the prior art.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The dimensionally stable polyester multifilament yarns made by the process of the present invention provide dimensionally stable treated cords when incorporated as fibrous reinforcement into rubber composites such as tires.
Dimensional stability is defined as high modulus at a given shrinkage and directly relates to tire sidewall indentations (SWI) and tire handling. While the modulus of the cord in the tire is the primary variable governing both SWI and handling, shrinkage is important in two ways. First, excessive cord shrinkage during tire curing can significantly reduce the modulus from that of the starting treated cord. Second, cord shrinkage is a potential source of tire non-uniformity. Thus, comparison of modulus and tenacity at a given shrinkage is a meaningful comparison for tire cords. Since tire cords experience deformations of a few percent during service, a good practical measure of modulus is LASE-5 (load at 5 percent elongation). Alternatively, E 4 .5 (elongation at 4.5 g/d load) can be used as a practical measure of compliance.
For both tire SWI and handling, modulus at elevated temperature (up to 110° C. ) is the important parameter governing performance. Due to the highly crystalline nature of treated cords based on conventional or dimensionally stable tire yarns, the modulus retention (in percent) at elevated tire temperatures is essentially similar for all current commercial treated cords and for those of this invention when loss modulus peaks occur at 110° C. or greater. Thus, room temperature measurement of LASE-5 is sufficient to establish meaningful differences in polyester cord dimensional stability.
The polyester yarn contains at least 90 mol percent polyethylene terephthalate (PET). In a preferred embodiment, the polyester is substantially all polyethylene terephthalate. Alternatively, the polyester may incorporate as copolymer units minor amounts of units derived from one or more ester-forming ingredients other than ethylene glycol and terephthalic acid or its derivatives. Illustrative examples of other ester-forming ingredients which may be copolymerized with the polyethylene terephthalate units include glycols such as diethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, etc., and dicarboxylic acids such as isophthalic acid, hexahydroterephthalic acid, bibenzoic acid, adipic acid, sebacic acid, azelaic acid, etc.
The polymer may be polymerized in a separate operation or polymerized in a directly coupled continuous polymerization and direct melt spinning process.
An important aspect of this invention permits obtaining high undrawn birefringence yarn without the need to utilize molecular weight enhancing additives such as multifunctional coupling agents exemplified by 2,2'-bis(2-oxazoline). Catalysts for the polymerization reaction are not considered to be included in the definition of molecular weight enhancing additive.
The multifilament yarn of the present invention commonly possesses a denier per filament of about 2.5 to 20 (e.g. about 3 to 10), and commonly consists of about 6 to 600 continuous filaments (e.g. about 20 to 400 continuous filaments). The denier per filament and the number of continuous filaments present in the yarn may be varied widely within the ranges of this invention as will be apparent to those skilled in the art.
The multifilament yarn made by the process is particularly suited for use in industrial applications including rubber composites, ropes, cordage and tarps. The fibers are particularly suited for use in environments where elevated temperatures (e.g. 80° C. to 100° C.) are encountered.
The yarn characterization parameters referred to herein may conveniently be determined by testing the multifilament yarn which consists of substantially parallel filaments.
Undrawn birefringence (Δn u ) was determined using a polarizing light microscope equipped with a Berek compensator.
Intrinsic viscosity (IV) of the polymer and yarn is a convenient measure of the degree of polymerization and molecular weight. IV is determined by measurement of relative solution viscosity (η r ) of PET sample in a mixture of phenol and tetrachloroethane (60/40 by weight) solvents. The relative solution viscosity (η r ) is the ratio of the flow time of a PET/solvent solution to the flow time of pure solvent through a standard capillary. Billmeyer approximation (J. Polym. Sci. 4, 83-86 (1949)) is used to calculate IV according to ##EQU1## where C is concentration in gm/100 ml. In this study, the concentration was 1.3 gms/100 ml. It will be understood that IV is expressed in units of deciliters per gram (dl/g), even when such units are not indicated. Comparison to IV measurements in other solvents is given in an article by C. J. Nelson and N. L. Hergenrother, J. Poly. Sci., 12 2905 (1974). The invention makes possible obtaining high modulus drawn yarn without the need to utilize exceptionally high IV polymer. Satisfactory drawn yarns with high Δn u with IV of at least 80, for example 0.85 to 0.95 can be obtained by this invention.
The tensile properties referred to herein were determined on yarns conditioned for two hours through the utilization of an Instron tensile tester (Model TM) using a 10-inch gauge length and a strain rate of 120 percent per minute in accordance with ASTM D885. All tensile measurements were made at room temperature.
Elongation at the specified load of 4.5 g/d (E 4 .5) is inversely related to modulus. It is particularly useful in that the sum E 4 .5 +FS is a good indicator of dimensional stability for yarns processed under different relaxation levels. Lower sums (E 4 .5 +FS) indicate better dimensional stability. Drawn yarn of the present invention is produced with Δn u greater yarn than 0.020 and posses a dimensional stability defined by E4.5+FS<16%. Free shrinkage (FS) values were determined in accordance with ASTM D885 with the exception that the testing load was 0.009 g/d. Such improved dimensional stability is of particular importance if the product serves as fibrous reinforcement in a radial tire.
Identified hereafter is a description of the continuous spin-draw process which has been found to be capable of forming the desired improved yarns. FIGS. 1 and 2 illustrate apparatus which may be utilized to practice the process of this invention, though it will be recognized by those of skilled in the art that the apparatus illustrated may be modified in known ways.
Referring to FIGS. 1 and 2, like numbers indicate like apparatus. Molten polymer is fed by extruder 11 to spin pump 12 which feeds spin block 13 containing a spinneret and a spinning filter disposed between the spin pump and spinneret. The spinneret is designed for the extrusion of one or more ends of filaments, each end containing a plurality of filaments. FIG. 1 illustrates the simultaneous extrusion of two ends 14 and 15 of multifilament, continuous filament yarn from one spinneret. Ends 14 and 15 are extruded from the spinneret at a spinning temperature in the range of 282 to 320° C. and at a desired polymer volumetric flowrate (Q, cm 3 /min/capillary), and are passed downwardly from the spinneret into a delay zone, chamber 16, which preferably is a quiescent delay zone or a heated sleeve of a desired delay length preferably 1 to 40 inches, maintained at a desired heated sleeve temperature preferably 100° to 450° C. Yarn leaving chamber 16 is passed directly into the top of the quenching zone, apparatus 17, preferably a radial inflow quench. The quench chamber is an elongated chimney of conventional length for example 1 to 40 inches. Ends 14 and 15 of yarn are lubricated by finish applicator 18. A spinning finish composition is used to lubricate the filaments. For the examples in this application, finish applicator 18 was a lube roll which is rotated with the direction of the yarn movement. Other means of applying finish could also be used.
To achieve desired properties in the final drawn yarn, it is necessary to hot draw the partially-oriented multifilament yarn withdrawn from the quenching zone, for example to at least 85 percent of the maximum draw ratio. This can be accomplished either in an off-line drawing process or preferably in a continuous spin-draw process. The drawing may be multiple steps and include high temperature annealing with or without relaxation. In this illustration, ends 14 and 15 are then transported to spin draw panel 21. A typical configuration is shown in FIG. 2. In FIG. 2, ends 14 and 15, are all processed on the same single set of forwarding (first roll 1), drawing (rolls 2-3 and rolls 5-6) and relaxing rolls (rolls 7-8). From draw roll 2, the ends are passed through a steam impinging draw point localizing steam jet 4. From relaxing rolls 7 and 8, the yarn ends are forwarded to winder 22. For the discussion following V is taken as the linear speed of roll 1.
With respect to conditions for operating the apparatus to achieve the process of this invention, it is generally known that undrawn birefringence (Δn u ) can be increased by increasing the spinning speed (V given in km/min) or the IV of the yarn (dl/g). By experimental work accomplished during the course of this invention, this can now be quantified by the following experimentally determined relationship:
Δn.sub.u =R.sub.f V.sup.2.0 IV.sup.2.4
V is the spinning speed given in kilometers/minute. IV is the intrinsic viscosity of the undrawn yarn given in dl/g. R f is a value characteristic of the additional processing variables other than V and IV. The ratio Δn u /IV 2 .4 is introduced to indicate the ability to achieve high Δn u for a given IV.
For conventional and prior art processes, R f is typically ≦8×10 -3 , whereas for the process of this invention R f is ≧9.0×10 -3 . Of course, the higher the R f value, the higher the undrawn birefringence for a given IV and V. Apparently, the combination of high molecular weight (IV>0.80) and inherent stiffness of the PET molecule results in a sufficiently slow relaxation rate in the molten state to achieve high R f values. High R f values, for example R 4 ≧15×10 -3 , are readily attainable by this invention and are of prime commercial interest. For more dimensionally stable products, it is preferred that Δn u /IV 2 .4 be at least 0.098.
R f can be broken down into two more basic terms:
R f =R r R e
R r is related to the retention in orientation after thermally induced polymer relaxation. This parameter increases with increasing severity of the quenching and decreases with increasing extruded polymer temperature and heated sleeve length and temperature. One skilled in the art can adjust these parameters to maximize Δn u and still maintain good spinnability.
The core of the invention is in the R e term which is related to the effective polymer extension from flow orientation in the spinneret and draw-down in the spin column. The net result is substantial orientation even at moderate spinning speeds. The experimentally determined relationship is ##EQU2## where D is the spinneret capillary diameter (inches) and Q is the polymer flow rate through the capillary expressed in cm 3 /min/capillary. Q is calculated using a polymer density of 1.2 gm/cm 3 . This invention also teaches the proper combination of D and Q to achieve R e of at least 10.5×10 -2 . More preferred, R e e is at least 13×10 -2 .
For D, a preferred diameter is at least 0.027 inches and less than 0.055 inches. This range represents an important processing range for optimizing fiber uniformity together with effective spinneret hole design options.
If one looks only at the IV range 0.80-0.95, a simplified expression may be obtained which shows the advantage of this invention over prior art, with Δn u of at least 7.0×10 -3 V 2 . It may be preferred to achieve even higher birefringence for a given V, with Δn u of at least 11.5×10 -3 V 2 . Thus, for this viscosity range, the invention can also be defined solely in terms of V.
The particular examples which follow show how proper selection of process variables results in R f ≧9.0×10 -3 and the desired improved yarns which exhibit improved dimensional stability. The comparative examples are taken from the patents previously cited and are summarized in Table I. This table contains all examples in which (a) the drawn yarn had a dpf of at least 2.5, (b) Δn u was at least 0.020, and (c) the yarn IV was between 0.85 and 0.96. The latter IV range was chosen since it is close to the 0.88-0.92 range in our examples.
EXAMPLE 1
PET polymer was pumped at 296° C. to a spinneret containing multiple orifices, each orifice of 0.030 inch diameter (D=0.030 inch). The extension rate per hole (Q) was 0.88 cm 3 /min. The filaments were passed through a 1-inch heated sleeve and then quenched in a radial quench stack. The spun yarn was subsequently drawn on a panel similar to FIG. 2, with roll 1 maintained at 90° C., the yarn drawn 1.5/1 to unheated rolls 2, 3 with a normal ambient temperature of 40°-50° C., then drawn 1.6/1 from rolls 2, 3 to rolls 5, 6 maintained at 200° C., the yarn was then relaxed to rolls 7, 8 at 1 to 1.5 percent. Rolls 7 and 8 had an operating temperature of 150° C. The drawn yarn was taken up at 2.98 km/min. Polymer thruput for the two ends was 85 lbs./hour. The drawn yarn was 1004 denier, 3.3 dpf, 17.5 lbs. breaking strength, 7.9 g/d tenacity, 10.6 percent ultimate elongation, 3.9 g/d LASE-5, 5.5% E 4 .5 and 9.2 percent FS. The sum E 4 .5 +FS is 14 percent. The undrawn yarn birefringence (Δn u ) was 0.026 and IV was 0.92 dl/g. R f was 24×10 -3 . The yarn produced in this example, while produced at a moderate spinning take-up speed usually associated with standard yarn products, is then shown to have that enhanced dimensional stability associated with substantially higher spinning speeds in the prior art. R f and R e were 24×10 -3 and 19×10 -2 , respectively.
EXAMPLE 2
An ultradimensionally stabilized PET was produced in the following manner. PET polymer was pumped into a spinneret containing multiple orifices, each orifice of 0.027 inch diameter (D=0.027 inch). Q was 1.3 cm 3 /min/cap. The filaments were then passed through a heated sleeve (HST=220°-300° C., residence time 0.02-0.03 sec) and quenched in a radial quench stack. The spun yarn was first drawn 1.4/1 between rolls at 90° C. and unheated rolls, then drawn 1.15/1 between these and rolls maintained at 220° C. The drawn yarn was then relaxed at 3% to rolls maintained at 135° C. The yarn was taken up by a high speed winder at 4.60 km/min. The drawn yarn was 924 denier, 3.3 dpf, 5.8 g/d tenacity, 4.1 g/d LASE-5, 6.5 percent E 4 .5, 10.3 percent ultimate elongation, 4.3 percent free shrinkage. The sum E 4 .5, +FS was 10.8 percent. The undrawn yarn birefringence was 0.082 and IV was 0.92 dl/g. R f was 11×10 -3 and R e was 14×10 -2 .
EXAMPLE 3
Yarn (IV=0.92) was produced in a similar manner to that in Example 1, only (a) a 2-inch sleeve was heated to 220°-300° C. (b) the spinneret orifice was 0.018 inch, and (c) Q was 1.0 cm 3 /min/cap. The drawn yarn was taken-up at 4.72 km/mins after experiencing a 2.46/1 hot draw ratio. This yarn had similar properties to Example I: 3.3 dpf, tenacity of 8.1 g/d, ultimate elongation of 10.0%, LASE-5 of 3.9 g/d, E 4 .5 of 5.5%, and free shrinkage of 10.0%. The 0.028 undrawn birefringence corresponded to a R f of 11×10 -3 . R e was 13×10 -2 .
EXAMPLE 4
A high viscosity yarn (IV=0.88) was prepared similar to Example 2 only D=0.018 inches and V=3.5 km/min. The undrawn yarn had a birefringence of 0.088 which corresponds to R f =9.8×10 -3 . Drawn dpf was 2.7 and R e was 11×10 -2 .
TABLE I______________________________________ V Prior Art Examples*ΔnIV(dl/g).sup.@ (km/min) R.sub.f (10.sup.-3) R.sub.e (10.sup.-2) Ref.______________________________________0.0210.96 2.0 5.9 7.7 U.S. Pat. No. 4,491,6570.0390.96 3.05 4.7 6.9 U.S. Pat. No. 4,491,6570.0520.96 3.5 4.7 6.7 U.S. Pat. No. 4,491,6570.0720.95 4.0 5.2 6.4 U.S. Pat. No. 4,491,6570.0880.95 4.5 4.8 6.4 U.S. Pat. No. 4,491,6570.0970.95 5.0 4.4 6.2 U.S. Pat. No. 4,491,6570.0730.90 3.5 7.5 8.9 U.S. Pat. No. 4,690,866______________________________________ *Includes only drawn dpf of at least 2.5 and IV between 0.85 and 0.96. .sup.@ 60:40 Phenol/Tetrachloroethylene solvent.
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A process for production of a dimensionally stable drawn polyethylene terephthalate multifilament yarn having filaments of at least 2.5 denier per filament comprising the steps of:
a) extruding a polyethylene terephthalate polymer melt through a spinnerette having a plurality of extrusion orifices to form filaments;
b) advancing the extruded multifilament yarn first through a delay zone then through a quenching zone to solidify the filaments in a controlled manner;
c) withdrawing the solidified multifilament yarn from the quenching zone at a desired spinning speed V;
whereby steps a) through c) are performed under conditions to form a partially-oriented multifilament yarn having a undrawn birefringence (Δn u ) of at least 0.020 and wherein Δn u =R f V 2 .0 IV 2 .4 where IV is the intrinsic viscosity of the undrawn yarn and is at least 0.80 and R f is at least 9.0×10 -3 ; then
d) hot drawing the partially-oriented multifilament yarn. The process permits production of high undrawn birefringence yanrs at lower speeds and lower IV's than previously demonstrated in the prior art.
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BACKGROUND
[0001] Devices (e.g., computing devices, communication devices, etc.) require various connectors and cables (e.g., communication cable connectors, power cords, etc.) to properly function. However, such connectors and/or cables may become disconnected from devices due to vibrations, earthquakes, accidental removal, etc. This may cause the devices to malfunction. For example, a communication cable or power cord may disconnect from a network device, which may cause the network device to cease transmitting and/or receiving network traffic.
SUMMARY
[0002] A retainer may include a hollow portion for holding a connector, a path for conveying the connector from outside the retainer to the hollow portion, a surface that is adjacent to the connector when the connector is held in the hollow portion, a fastener for applying a force to couple the retainer to a device, and a member that causes the surface to press the connector against a connector receiver associated with the device and to prevent the connector from being disengaged from the connector receiver.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate one or more implementations described herein and, together with the description, explain these implementations. In the drawings:
[0004] FIG. 1 is a diagram illustrating an isometric view of an exemplary system in which a connector retaining bracket described herein may be implemented;
[0005] FIG. 2A-2D are isometric, top, front, and side views, respectively, of the bracket illustrated in FIG. 1 ;
[0006] FIG. 3 is a side view of a thumb screw illustrated in FIG. 1 ; and
[0007] FIG. 4 is a flowchart of an exemplary process for applying a connector retaining bracket according to implementations described herein.
DETAILED DESCRIPTION
[0008] The following detailed description refers to the accompanying drawings. The same reference numbers in different drawings may identify the same or similar elements. Also, the following detailed description does not limit the invention.
[0009] Systems and methods described herein may provide a connector retaining bracket to ensure a continued attachment of a connector and/or a cable to a device. In one implementation, the device may include a connector receiver configured to receive the connector, and the connector may connect to the device via the connector receiver.
[0010] The connector retaining bracket may include a bracket and fasteners. The bracket may fit around and hold the connector, which is connected to the connector receiver. The fasteners may affix the bracket to the device to which the connector receiver is attached. The tension with which the bracket retains the connector in place may be applied by the fasteners. Consequently, the connector retaining bracket may prevent the connector from disconnecting from the device.
Exemplary System
[0011] FIG. 1 is a diagram illustrating an isometric view of an exemplary system 100 in which a connector retaining bracket described herein may be implemented. As illustrated, system 100 may include a device 102 (that includes a panel 108 , a connector receiver 110 , and fastener supports 112 (only one fastener support is shown)), a connector 104 , connector cords 106 , a bracket 114 , and fasteners 116 - 1 and 116 - 2 .
[0012] Device 102 may include a network device (e.g., a gateway, a router, a switch, a firewall, a network interface card (NIC), a hub, a bridge, a proxy server, or some other type of device that processes and/or transfers data), a computation or communication device (e.g., a laptop, a personal computer, a work station, a server, etc.), a mobile communication device (e.g., e.g., a personal communications system (PCS) terminal, a personal digital assistant (PDA), a cellular telephone, etc.), and/or any other device capable of receiving a connector, such as connector 104 . Although device 102 is shown in FIG. 1 as including panel 108 , connector receiver 110 , and screw supports 112 , in other implementations, device 102 may include additional components (not shown) depending upon the function of device 102 .
[0013] Connector 104 may include a communication cable connector (e.g., peripheral component interface (PCI) express (PCIE) connector, a Universal Serial Bus (USB) connector, etc.), a power cord connector (e.g., a power supply connector, a plug, etc.), an eight position, eight conductors (8P8C or “RJ45”) connector, a nine-pin D-shell (DE-9) connector, an optical connector (e.g., a standard connector (SC), a ferrule connector (FC), a sub miniature A (SMA) connector, etc.), a telephone connector, etc.), etc.
[0014] Connector cords 106 may include cords connected to connector 104 . For example, connector cords 106 may include PCIE cables, a power cord, etc., that may provide electrical signals, optical signals, communication signals, power, etc. to device 102 via connector 104 , depending upon the function of connector 104 .
[0015] Panel 108 may include a surface on device 102 or a portion of the surface to which connector receiver 110 and/or screw supports 112 may be affixed or mounted. Panel 108 may be made of the same material as a housing for device 102 (e.g., sheet metal, plastic, etc.) and may be capable of rigidly supporting connector receiver 110 and/or screw support 112 . For example, panel 108 may substantially maintain the flatness of its shape when connector 104 is inserted into connector receiver 110 and thumb screws 116 - 1 and 116 - 2 are inserted into screw holes in screw supports 112 and tightened.
[0016] Connector receiver 110 may include a mechanism that is sized, shaped, and/or configured to receive connector 102 . For example, if connector 110 is a male PCIE connector, connector receiver 110 may be sized and shaped to receive the size and shape of the PCIE connector, and may include a socket to receive pins for a ground, a positive connection (e.g., +12 volt), a negative connection that may connect with a corresponding ground, a clock, data, etc. Connector receiver 110 may attach connector 104 to internal components of device 102 , and may enable connector 104 to communicate (e.g., electrically communicate, optically communicate, etc.) with device 102 . Depending on the implementation, connector receiver 110 may accommodate connectors of different dimensions and configurations (e.g., an 18-pin male/female PCIE connector, 32-pin male/female PCIE connector, etc.).
[0017] Fastener supports 112 may include a component that is mounted and/or affixed to panel 108 and may provide a feature to which fasteners 116 - 1 and 116 - 2 may latch or be attached to. In one implementation, fastener supports 112 may be implemented as screw supports. In such an implementation, the flat surface on fastener supports 112 may include a threaded screw hole (not shown) through which a thumb screw may be inserted via a portion of bracket 114 . Once the thumb screws are inserted and tightened, bracket 114 may be coupled rigidly and stably against device 102 . In a different implementation, fastener supports 112 may include latches to which springs attached to the bracket may be locked/fastened. Locking the springs may couple the bracket 114 rigidly and stably against device 102 . While many different mechanisms may be used to provide the functionalities of fastener supports 112 , however, in the following descriptions, fastener supports 112 will be described in terms of screw supports.
[0018] Bracket 114 may receive connector 104 and apply a force on connector 104 against connector receiver 110 to ensure that connector 104 remains connected to connector receiver 110 of device 102 . In one implementation, bracket 114 may resemble a rectangular plastic box that includes a cavity for receiving connector 104 and connector cords 106 . Bracket 114 may be implemented in a variety of shapes and sizes depending upon the size and shape of connector 104 . For example, in one implementation, bracket 114 may be small in size if connector 104 is small (e.g., a telephone connector), and may be large in size if connector 104 is large (e.g., a power cord connector).
[0019] Bracket 114 may be made from a variety of materials, such as a thermoplastic polymer (e.g., a polycarbonate resin, polyethylene, polypropylene, polyvinyl chloride, a fluoroplastic, etc.), a metal or metal alloy (e.g., stainless steel, copper, iron, nickel, zinc, brass, bronze, aluminum, etc.), a combination of the aforementioned materials, etc. Further details of bracket 114 are provided below in connection with FIGS. 2A through 2D .
[0020] Each of fasteners 116 - 1 and 116 - 2 may be attached to their respective fastener supports 112 to affix bracket 114 against device 102 . In one implementation, each of fasteners 116 - 1 and 116 - 2 may be implemented as thumb screws. In such an implementation, each of the thumb screws through a cylindrical tube portion of bracket 114 and into a screw hole in screw supports 112 . By rotating each of the thumb screws, the cylindrical portion of bracket 114 and/or connector 104 may be forcibly abutted against edges of connector receiver 110 and/or fastener support 112 , preventing connector 104 from becoming loose. In another implementation, wire springs may be used in place of the thumb screws. In such a case, latching the springs to fastener support 112 may apply the necessary force on bracket 114 to prevent connector 104 from becoming detached from connector receiver 110 . While many different mechanisms can be used to apply the force on bracket 114 in different implementations, however, in the following, fasteners 116 - 1 and 116 will be described in terms of thumb screws.
[0021] Although FIG. 1 shows exemplary components of system 100 , in other implementations, system 100 may contain fewer, different, or additional components than depicted in FIG. 1 . In still other implementations, one or more components of system 100 may perform one or more of the functions described as performed by one or more other components of system 100 .
Exemplary Connector Retaining Bracket Configuration
[0022] FIGS. 2A through 2D are isometric, top, front, and side views, respectively, of bracket 114 that uses thumb screws as fasteners 116 - 1 and 116 - 2 . As illustrated in FIGS. 2A-2D , bracket 114 may include a left wall portion 202 - 1 , a right wall portion 202 - 2 , a bottom wall portion 204 , a guard panel portion 206 , a left cylindrical tube portion 208 - 1 , a right cylindrical tube portion 208 - 2 , a left fin portion 210 - 1 , a right fin portion 210 - 2 , a left front wall portion 212 - 1 , and a right front wall portion 212 - 2 . In one implementation, the portions may be integrally formed together (e.g., via molding, extrusion, casting, etc.). In another implementation, the portions may be connected together via a variety of connection mechanisms (e.g., via adhesives, glue, solder, screws, and/or similar connection mechanisms). In yet another implementation, guard panel portion 206 , left fin portion 210 - 1 , and right fin portion 210 - 2 of bracket 114 may, or may not, include uniform thickness. In one example, guard panel portion 206 may include a portion whose thickness ranges from about 0.2 millimeter to about 1.5 millimeter.
[0023] Left wall portion 202 - 1 , bottom wall portion 204 , left front wall portion 210 - 1 , right front wall portion 210 - 2 , and right wall portion 202 - 2 may be adjoined to form a cavity 214 . Left wall portion 202 - 1 may be adjoined perpendicularly to left front wall portion 210 - 1 and bottom wall portion 204 , and right wall portion 202 - 2 may be adjoined perpendicularly to right front wall portion 210 - 2 and bottom wall portion 204 .
[0024] The lengths of the adjoined wall portions may be set such that connector 104 may substantially fit snugly into cavity 214 , as illustrated in FIG. 1 . Depending on the implementation, the dimensions of left wall portion 202 - 1 , bottom wall portion 204 , left front wall portion 210 - 1 , right front wall portion 210 - 2 , and right wall portion 202 - 2 may be designed to fit the shape of a particular type of connector. For example, in one implementation, length X ( FIG. 2B ), width Y ( FIG. 2B ), and height Z may be set to about 60 millimeters, 59 millimeters, and 8 millimeters, respectively, so that the wall portions may form a cavity into which a PCIE connector may fit.
[0025] In forming cavity 214 , left wall portion 202 - 1 , right wall portion 202 - 2 , and bottom wall portion 204 may be cut and shaped to increase the maneuverability of connector 104 when connector is being fitted into or is being removed from cavity 214 of bracket 114 .
[0026] For example, bottom wall portion 204 , as shown in FIGS. 2A and 2B , may include a rectangular slot 218 . To fit connector 104 into cavity 214 , connector 104 may be inserted through open space 216 in the direction of arrow 222 - 1 and through cavity 214 in the direction of arrow 222 - 2 . In inserting connector 104 through open space 216 , because the width of open space 216 may be shorter than the width of connector 104 , connector 104 may be oriented such that a narrow side of connector 104 may face the same direction as guard panel portion 206 . To further move connector 104 through open space 216 and into cavity 214 , rectangular slot 218 may be formed on bottom wall portion 204 . Via rectangular slot 218 , connector 104 may easily move through open space 216 and cavity 214 .
[0027] In another example, as shown in FIG. 2D , the top edge of right wall 202 - 2 may be cut, as shown by a dotted ellipse 224 . In removing bracket 114 from connector 104 , connector 104 may be easily separated from bracket 114 if connector 104 can be held apart from bracket 114 . To facilitate such an action, part of right wall portion 202 - 1 and left wall portion 202 - 2 may be cut and removed. As indicated by dotted ellipse 224 in FIG. 2D , a portion of right wall 202 - 2 may be removed, so that when connector 104 is fitted into cavity 214 in bracket 114 , part of connector 104 may be accessible, as the obstructing wall portion has been removed.
[0028] When connector 104 is being fitted into cavity 214 , once connector 104 has been initially pushed through open space 216 and placed around cavity 214 in the direction of arrow 222 - 2 , connector 104 may be rotated and/or realigned, such that the side flat surfaces of connector 104 are substantially parallel to left side wall portion 202 - 1 , right side wall portion 202 - 2 , and bottom wall portion 204 . Once connector 104 is in the proper orientation, connector 104 may be fitted or snapped into cavity 214 .
[0029] Guard panel portion 206 may be perpendicularly adjoined to the top edge of left wall portion 202 - 1 , right wall portion 202 - 2 , left front wall portion 212 - 1 , and right front wall portion 212 - 2 . In addition, guard panel portion 206 may be cut or shaped to expose a top surface of connector 104 that is placed in cavity 214 . In such instances, connector 104 may be easily placed in or removed from cavity 214 .
[0030] In addition, guard panel portion 206 may include a portion that may extend over cords 106 when connector 104 is fitted into cavity 214 . By the virtue of the extension, panel portion 206 may deflect a blow or an impact to cord 106 . Without guard panel portion 206 , such a blow or an impact may damage or cause connector 104 and/or cord 106 to be separated from one another and/or connector receiver 110 .
[0031] Left cylindrical tube portion 208 - 1 and right cylindrical tube portion 208 - 2 may be adjoined lengthwise to left wall portion 202 - 1 and right wall portion 202 - 2 , respectively. Furthermore, each of left cylindrical tube portion 208 - 1 and right cylindrical tube portion 208 - 2 may be hollow, such that fasteners 116 - 1 and 116 - 2 may be inserted into and through left cylindrical tube portion 208 - 1 and right cylindrical tube portion 208 - 2 . As shown in FIG. 1 , if bracket 114 is placed against panel 108 such that connector 104 is inserted into connector receiver 110 and holes in left and right cylindrical tube portions 208 - 1 and 208 - 2 are aligned against screw holes in fastener supports 212 , fasteners 116 - 1 and 116 - 2 (e.g., thumb screws) through left and right cylindrical tube portions 208 - 1 and 208 - 2 may be inserted into screw holes in fastener supports 112 and rotated to press connector 104 against connector receiver 110 .
[0032] Being made of the rigid material, when fasteners 116 - 1 and 116 - 2 are tightened, the heads of fasteners 116 - 1 and 116 - 2 (e.g., heads of thumb screws) may press against left cylindrical tube portion 208 - 1 and right cylindrical tube portion 208 - 2 . Left cylindrical tube portion 208 - 1 and right cylindrical tube portion 208 - 2 may impart a resulting force to left wall portion 202 - 1 and right wall portion 202 - 2 , which consequently may distribute the force to other portions of bracket 114 . Consequently, left and right front wall portions 212 may push connector 104 in cavity 214 against connector receiver 110 , to prevent connector 104 from becoming separated or unplugged from connector receiver 110 .
[0033] Depending on the implementation, left and right cylinder tube portions 208 - 1 and 208 - 2 may include slots 220 that render portions of thumb screws 116 - 1 and 116 - 2 visible when thumb screws are placed in left and right cylinder tube portions 208 - 1 and 208 - 2 . In such cases, if one or both of thumb screws 116 - 1 and 116 - 2 break, the breaks may be visible through slots 220 . A user that sees the damages may take corrective actions.
[0034] Left fin portion 210 - 1 and right fin portion 210 - 2 may be adjoined to top edges of left front wall portion 212 - 1 and right front wall portion 212 - 2 . Left fin portion 210 - 1 and right fin portion 210 - 2 may be sized and positioned perpendicularly underneath guard panel portion 206 such that guard panel portion 206 , left fin portion 210 - 1 , and right fin portion 210 - 2 may provide for enough open space 216 to accommodate cords 216 attached to connector 104 when connector 104 is fitted into cavity 214 . In addition, left fin portion 210 - 1 and right fin portion 210 - 2 may extend from left front wall portion 212 - 1 and right wall portion 212 - 2 to protect cord 106 from inadvertent touches, impact, blows, etc. in lateral directions.
[0035] Although FIGS. 2A through 2D show exemplary portions of bracket 114 , in other implementations, bracket may contain fewer, different, or additional components than depicted in FIGS. 2A-2D . For example, in implementations that use wire springs to fasten bracket 114 to device 102 , bracket 114 may not include left and right cylindrical tube portions 208 - 1 and 208 - 2 . In still other implementations, one or more portions of bracket 114 may perform one or more of the functions described as being performed by one or more other portions of bracket 114 .
Exemplary Fasteners
[0036] FIG. 3 is a side view of fastener 116 - 1 / 116 - 2 that is implemented as a thumb screw. As illustrated in FIG. 3 , fastener 116 - 1 / 116 - 2 may include a threaded portion 302 , a beam portion 304 , and a head portion 306 . Depending on implementation, fastener 116 - 1 / 116 - 2 may include additional or different portions than those illustrated in FIG. 3 .
[0037] Threaded portion 302 of fastener 116 - 1 / 116 - 2 may include threads 308 and spaces 310 . One or more threads 308 may be provided in threaded portion 302 , and one space 310 may be provided between adjacent threads 308 . Threads 308 and spaces 310 may be configured similar to threads and spaces provided on a bolt or a screw. For example, threads 308 and spaces 310 may be provided in a helical configuration as either right-handed threads or left-handed threads.
[0038] Beam portion 304 may include a cylindrical portion that connects threaded portion 302 to head portion 306 .
[0039] Head portion 306 of fastener 116 - 1 / 116 - 2 may include a portion that is configured to have a diameter larger than that of beam portion 304 and may be sized to enable a user to manipulate (e.g., rotate clockwise or counter-clockwise) fastener 116 - 1 / 116 - 2 with one or more digits (e.g., a thumb and a finger) of the user's hand.
[0040] In some implementations, head portion 306 may include one or more grooves that may be formed on a peripheral surface of head portion 306 , and may sized to enable a user to manipulate (e.g., rotate clockwise or counter-clockwise) fastener 116 - 1 / 116 - 2 with one or more digits (e.g., a thumb and a finger) of the user's hand. Such grooves may provide traction for the user's grip and permit the user to turn fastener 116 - 1 / 116 - 2 with forces applied by the thumb and the finger. Although not shown in FIG. 3 , in other implementations, head portion 306 may include one or more slots that form a drive design (e.g., a flathead, a Phillips head, a hex design, etc.). The drive design may be manipulated by a corresponding mechanism (e.g., a flathead screwdriver, a Phillips head screwdriver, an Allen wrench, etc.) so that a user may manipulate (e.g., rotate clockwise or counter-clockwise) fastener 116 - 1 / 116 - 2 .
[0041] In operation, threaded portion 302 and beam portion 304 may be inserted through a hole in cylindrical tube portion 208 - 1 of bracket 114 while connector 104 is placed in cavity 214 . In such a configuration, threaded portion 302 may be aligned with one of fastener supports 112 . When head portion 306 of fastener 116 - 1 / 116 - 2 is turned, a forced applied by a user to turn fastener 116 - 1 / 116 - 2 may cause head portion 306 of fastener 116 - 1 / 116 - 2 to move toward fastener support 112 . This may increase a force applied by bracket 114 on connector 104 . Turning fastener 116 - 1 / 116 - 2 (with right-handed threads) counter-clockwise may cause head portion 306 of fastener 116 - 1 / 116 - 2 to move away from screw support 112 and may cause bracket 114 to move away from connector receiver 110 and/or fastener support 112 . This may decrease a force applied by bracket 114 on connector 104 . If threads 308 are left-handed threads, the reverse of the above example may occur.
[0042] Although FIG. 3 shows exemplary components of fastener 116 - 1 / 116 - 2 when fastener 116 - 1 / 116 - 2 is implemented as a thumb screw, fastener 116 - 1 / 116 - 2 in other implementations may contain fewer, different, or additional components than depicted in FIG. 3 . In still other implementations, one or more portions of fastener 116 - 1 / 116 - 2 may perform one or more of the functions described as being performed by one or more other portions of fastener 116 - 1 / 116 - 2 .
Exemplary Process
[0043] FIG. 4 depicts a flowchart of an exemplary process 400 according to implementations described herein. As shown in FIG. 4 , process 400 may begin with insertion of connector 104 through open space 216 and cavity 214 of bracket 114 (block 402 ). As described above, inserting connector 104 through open space 216 that is formed by left fin portion 210 - 1 , right fin portion 210 - 2 and guard panel 206 may entail turning or rotating connector 104 until connector 104 can move through rectangular slot 218 on bottom wall portion 204 of bracket 114 . Because a cord may be attached to connector 104 , moving connector 104 through open space 214 and cavity 214 may also move the cord through open space 214 and cavity 216 .
[0044] Connector 104 may be oriented such that connector 104 can be snapped into cavity 214 (block 404 ). Connector 104 may be placed or fitted into cavity 214 (block 406 ). A user may place connector 104 in cavity 214 until a rear surface of connector 104 presses against left and right front walls 212 - 1 and 212 - 2 of bracket 114 .
[0045] Connector 104 that is placed/fitted within bracket 114 may be inserted into connector receiver 114 (block 408 ). In one implementation, connector 104 may include female/male connector portion that may be plugged into male/female connector receiver 110 .
[0046] Each of two fasteners 116 - 1 and 116 - 2 may be inserted through part of bracket 114 to be attached to a fastener support (block 410 ). In one implementation, two fasteners 116 - 1 and 116 - 2 may include thumb screws, and each of the thumb screws may be inserted through a corresponding one of cylindrical tube portions 208 - 1 and 208 - 2 into a screw hole in one of fastener supports (block 410 ).
[0047] At block 412 , each of fasteners 116 - 1 and 116 - 2 may be tightened (block 412 ). As described above, if fasteners are implemented as thumb screws, turning each of fasteners 116 - 1 and 116 - 2 may increase the force exerted on connector 104 against connector receiver 110 and/or the force exerted by bracket 114 against screw supports 112 .
CONCLUSION
[0048] The above describes a connector retaining bracket that may render a connector which may be easily detached from a connector receiver capable of being securely connected to the device. However, the foregoing description provides illustration and description, but is not intended to be exhaustive or to limit the embodiments to the precise form disclosed. Modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention.
[0049] For example, while a series of blocks has been described with regard to the flowcharts of FIG. 4 , the order of the blocks may differ in other implementations. Further, non-dependent blocks may be performed in parallel.
[0050] Even though particular combinations of features are recited in the claims and/or disclosed in the specification, these combinations are not intended to limit the invention. In fact, many of these features may be combined in ways not specifically recited in the claims and/or disclosed in the specification.
[0051] No element, act, or instruction used in the present application should be construed as critical or essential to the invention unless explicitly described as such. Also, as used herein, the article “a” is intended to include one or more items. Where only one item is intended, the term “one” or similar language is used. Further, the phrase “based on” is intended to mean “based, at least in part, on” unless explicitly stated otherwise.
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A retainer may include a hollow portion for holding a connector, a path for conveying the connector from outside the retainer to the hollow portion, a surface that is adjacent to the connector when the connector is held in the hollow portion, a fastener for applying a force to couple the retainer to a device, and a member that causes the surface to press the connector against a connector receiver associated with the device and to prevent the connector from being disengaged from the connector receiver.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 60/452,271, filed in the United States Patent and Trademark Office on Mar. 5, 2003, the entirety of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Technical Field
The present invention relates to the field of health care and, more particularly, to health care computer information systems that manage physiologic and treatment data.
2. Description of the Related Art
Most health care facilities, such as intensive care units (ICUs), acquire bedside patient information using pen and paper methodologies, such as flowsheets and patient charts. A flowsheet is a spreadsheet-type data matrix representing clinical observations over time. The paper documents used by health care facilities can include patient physiologic data, dates and times that the physiologic data was recorded, patient medications, symptoms, treatments, and clinical observations. For example, patient status information is periodically detected by bedside machines and recorded onto flowsheets by staff for a treating physician to later examine. Portions of these flowsheets can be manually entered into information systems to preserve patient information for administrative and research purposes. Further, paper documents containing physiologic data may require storage for a predefined period for record keeping purposes. Appreciably, the practice of recording and storing physiologic data on paper can be very time-consuming and expensive. Additionally, transcription errors can occur when using paper methodologies, which can result in improper treatment.
These shortcomings in managing physiologic data can be highly problematic. Physician decisions concerning patient treatments can be dependant upon the physiologic data available to the physician. The environment in which the physician works is complex, fast-paced, and is often crowded with both people and devices. Physicians can be summoned from one task to another, more urgent one, in seconds and can occasionally be required to rapidly analyze and treat patients with which the physician is only minimally familiar. In such situations, even the most accurate physiologic data can be useless to a physician if the physiologic data is presented in a confusing manner that takes concentration and time to find and comprehend. If patient data is inaccurate or misinterpreted, improper decisions can be made that can result in life altering consequences. Accordingly, the patient data upon which decisions are based should be presented in a clear, consistent, and comprehensible fashion. Further, the patient data should be available and accessible at the treatments or decision making location in order to be of use.
Another problem that exists with the conventional handling of physiologic data relates to clinical research. In order for clinical researchers to gather physiologic data, the researchers must acquire the paper documents upon which the physiologic data of patients has been recorded. The paper documents can include patient charts and flowsheets. Data from these paper documents can then be manually entered into a computing device so that the physiologic data contained within can be analyzed. This manual data entry process consumes substantial human resources and increases the likelihood of typographical errors. Further, clinical researchers will often be unaware of potentially valuable cases, since the only information sources for these cases can be paper documents, which may be difficult to search. Moreover, the paper documents from which data entry is conducted can contain confidential and/or sensitive patient information. This sensitive information can either limit the physiologic data available for clinical research purposes and/or induce additional data entry difficulties, such as requiring data entry to occur within a secure location.
One reason pen and paper methodologies have been conventionally used for recording physiologic data can relate to data integration difficulties. Presently, most physiologic data is recorded from bedside machines that monitor patients. These bedside machines generally lack the interfaces, such as an Ethernet or other network port, and/or communication standards, such a TCP/IP (Transmission Control Protocol/Internet Protocol) through which networking occurs. The only data port typically included with a bedside machine is a serial or parallel port, such as an RS-232 port. While such a data port can receive and accept data streams, these data streams follow no open standards, i.e. each bedside machine can transmit data in a proprietary manner using different data formats and protocols. In order for a computing device to communicate with a bedside machine via a data port, a tailored application must be uniquely written for that particular type of bedside machine. Present bedside machines are not packaged with software applications that facilitate communication via the data port.
A few systems do exist which can centrally present physiologic data gathered from multiple sources. These systems, however, typically exchange information in a propriety manner and can only communicate with other bedside machines which use the same proprietary protocol, i.e. other machines from a particular product line of a common manufacturer. Physiologic data from sources external to these proprietary monitoring systems, i.e. other manufacturer's bedside machines, cannot be integrated with the data contained within the proprietary monitoring systems. For example, the same type of bedside machine(e.g. a ventilator) made by a different manufacturer than the manufacturer of the proprietary monitoring system cannot be integrated with the proprietary system. Consequently, to achieve even the minimal data sharing capabilities provided by these proprietary networks, a health care provider is “locked into” a single bedside machine series or a single product line of a manufacturer. One effect of this lock-in can be a lack of a competitive marketplace resulting in higher costs and fewer monitoring options.
Presently, some systems are available to acquire data from bedside machines, however, these systems tend to utilize a proprietary physical connection and do not address unit workflow issues which is a core part to the present invention. Moreover, the presentation mechanisms for physiologic data cannot be configured so that physiologic data is presented in a manner designed to optimize physician comprehension. Further, conventional systems that monitor physiologic data do not provide mechanisms to facilitate data extraction to be used for clinical research.
SUMMARY OF THE INVENTION
The invention disclosed herein utilizes data synthesis technology (DST) to integrate physiologic data from at least one bedside machine with data from other data sources, such as computerized laboratory information systems. More particularly, a bedside computing device can be communicatively linked to at least one bedside machine via a data port, such as a RS-232 port. The bedside computing devices can include device drivers written for the various bedside machines with which the bedside device can communicate. Physiologic data, such as laboratory data, pharmacological data, care facility data, and bedside machine data, can then be presented within the bedside computing device in a configurable fashion within a single interface. The bedside computing device can be communicatively linked to a trusted network including care facility computing resources. The data protocols used by different computing devices and bedside machines can be synchronized to one another and stored into a local database and/or a centralized data repository. Additionally, synchronized data can be filtered for multiple health related purposes. For example, clinical research facilities can access stored patient physiologic data that has been filtered so that patient privacy information and identification has been removed.
One aspect of the present invention can include a method of integrating physiologic data that seamlessly complements the existing workflow process. The method can include receiving physiologic data from at least two bedside machines and converting the physiologic data into a machine independent format that is dynamically matched with discreet workflow data elements. For example, a data stream can be received from each of the bedside machines and a transport protocol particular to one of the bedside machines can be determined for each data stream. Thereafter, the data stream can be segmented into discrete elements. In one embodiment, for each of the discrete elements, a cross reference table can be utilized to determine a standard data format associated with the discrete element. At least a portion of the discrete elements can then be converted into the standard data format. The physiologic data can then be presented. In another embodiment, patient specific information can be removed from the physiologic data for clinical research use. In yet another embodiment, the method can respond to a user-driven request in perceptual real-time. For example, a user can request data and/or trend reports and be quickly presented with the requested data and/or trend reports. Such a data presentation will occur even if the data and/or trend reports relate to real-time physiologic data for presently monitored patients.
Another aspect of the present invention can include a system for integrating physiologic data. The system can include a bedside machine for monitoring physiologic data that includes a data port for serial communication. A bedside computing device can be communicatively linked to the bedside machine through the data port and communicatively linked to a network through a network port. The system can also include a centralized data repository that is communicatively linked to the bedside computing device through the network port, wherein the centralized data repository is configured to synchronize data from a plurality of bedside machines, and wherein at least a portion of the bedside machines utilize different data conventions. An additional physiologic data source, such as a care network information system, a laboratory information system, and/or a pharmacy information system, can also be included. In one embodiment, at least a portion of the data from the bedside machines can be accessed by a clinical research facility after the data is “scrubbed” and replicated to the centralized data repository.
Another aspect of the present invention can include a system for integrating bedside physiologic data including at least two bedside machines, each configured to monitor at least one physiological condition. Each bedside machine can include a data port. A bedside computing device can be configured to present data from the bedside machines. The bedside computing device can include a data port and a network port. Additionally, the bedside computing device can be communicatively linked to the bedside machines through the data ports. In one embodiment, the bedside computing device can include at least one bedside machine driver configured for particular ones of the bedside machines. Each bedside machine driver can facilitate data exchanges between the bedside machines and the bedside computing device. The bedside computing device can also be configured to communicate physiologic data with a data source such as a laboratory information system, a hospital information system, and a pharmacy information system.
BRIEF DESCRIPTION OF THE DRAWINGS
There are shown in the drawings embodiments, which are presently preferred, it being understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown.
FIG. 1 is a schematic representation of a system for integrating physiologic information in accordance with the inventive arrangements disclosed herein.
FIG. 2 is a schematic representation of an integration system for integrating physiologic information within the system of FIG. 1 .
FIG. 3 is an exemplary graphical user interface showing flowsheet data for patient information using the system of FIG. 2 .
FIG. 4 is an exemplary graphical user interface showing flowsheet data for patient fluids using the system of FIG. 2 .
FIG. 5 is an exemplary graphical user interface showing data for multiple bedside machines using the system of FIG. 2 .
FIG. 6 is an exemplary graphical user interface for setting up a flowsheet display using the system of FIG. 2 .
FIG. 7 is an exemplary graphical user interface for setting up a trend display using the system of FIG. 2 .
FIG. 8 is an exemplary graphical user interface showing trends using the system of FIG. 2 .
DETAILED DESCRIPTION OF THE INVENTION
The invention disclosed herein provides a method, system and an apparatus for integrating physiologic data, which can be generically referred to as providing physiologic data using data synthesis technology (DST). More particularly, data streams can be conveyed between bedside machines that monitor physiologic data and a computing device communicatively linked to a network. The computing device can interpret the data streams sent from specified machines and transport the information contained within the data streams to a networked element. This networked element can transform the information into a machine-independent data schema. The information provided by bedside machines and other patient relative information, such as pharmacological data and laboratory results can be integrated within a single presentation device. For example, a bedside computing device can contain physiologic, laboratory, pharmacy, and other patient-centric data for a given patient. Additionally, physiologic data can be analyzed by other health-related systems. For example, clinical research facilities can access stored patient physiologic data that has been sanitized so that patient privacy information and identification has been removed.
As used herein, bedside refers to an environment in close proximately to a patient being treated. Items placed within a bedside environment should be near enough to the patient that a physician treating the patient can access the items while treatment is being performed. It should be noted that a bedside environment need not include a bed. For example, instead of a bed, a patient can be contained within an incubator, an ambulance, a gurney, a cot, an operating table, and the like. The term bedside should be liberally construed. For example, an apparatus which monitors conditions within the bedside environment, yet which is at least partially disposed outside the environment around the patient can, nevertheless, be considered a bedside apparatus. Similarly, an apparatus that can provide information to an individual, such as a physician, located within the bedside environment can be considered bedside apparatus even if necessary portions of the apparatus are in a location remote from the patient.
FIG. 1 is a schematic representation of a system 100 for integrating physiologic data in accordance with the inventive arrangements disclosed herein. The system 100 can include an integration system 105 , a bedside machine 110 , a hospital information system 115 , a laboratory information system 120 , a pharmacy information system 125 , a remote access device 130 , and a research information system 135 . The integration system 105 can receive information, including physiologic information, from multiple sources, transform the information into data elements formatted according to a database schema, and convey these data elements to a variety of customized applications.
The integration system 105 can store all patient information for a particular hospital within one or more data stores, such as research data store 140 and patient data store 145 . By using different data stores, privacy considerations can be handled automatically without extensive human intervention and/or costs. Notably, the various data stores of the integration system 105 can include data from a multiplicity of different databases that are continuously or periodically synchronized to one another. Each of these databases can utilize the same or different information structures. When diverse information structures are included within the integration system 105 , a data warehouse can help reconcile differences among data elements.
The bedside machine 110 can be a sensor of physiologic data that can determine one or more parameters relating to the health of a patient. The bedside machine 110 can include a blood gas monitor, an infusion pump, a physiological monitor, a pulse oximeter, a flowmeter, a ventilator, an automated patient care bed, a thermocouple probe, and the like. The bedside machine 110 can also include a data port for electronically conveying the physiologic information to connected computing devices. If a data port is not originally included within the bedside machine 110 , then one can be retrofitted to the bedside machine 110 . The data port can communicate via a physically connected cable or though a wireless transmission means, such as radio frequency. Notably, the bedside machine 110 can be a device integrated within other bedside machines and/or can be a standalone device. The bedside machine 110 can be any one of a plurality of devices that detect physiological parameters for patients, i.e. as typically located in a care taking facility, such as an intensive care unit (ICU). Further, multiple bedside machines 110 that monitor a patient can be connected to the integration system 105 . Physiologic data from the multiple monitors can be simultaneously displayed on a single presentation device within the integration system 105 .
The hospital information system 115 can be the information system used by a health care provider that contains patient and staff information. The hospital information system 115 can include, but is not limited to, patient medical records, a reference table between treating physicians and patients, patient contact information, physician contact information, and important patient medical annotations, such as allergies, blood type, donor status, and other medical attributes for patients. The hospital information can also contain information concerning employees working specified shifts, on-call physicians, and alternative treating physicians for particular patients.
The laboratory information system 120 can be the information system used by a medical laboratory. The laboratory information system 120 can include information related to conducted tests, such as the date of a test, a patient identifier, a sample identifier, methodologies used, examiner information, test results, and other test annotations. A laboratory information system 120 can be integrated within another information system, such as the hospital information system 115 , or can function autonomously. Further, the laboratory information system 120 can be a system limited to a particular laboratory, or can contain information from a multitude of laboratories located at the same or different locations.
The pharmacy information system 125 can be an information system used to record patient prescription information. For example, the pharmacy information system 125 can contain a date for a prescription, prescription strength, prescription dosage, prescribing physician, patient, number of refills, known drug side effects and warnings, and the like. The pharmacy information system 125 can be an integrated system containing information from many different pharmacies or can be restricted to a particular pharmacy, such as one within a hospital or treating facility.
The remote access device 130 can include any device communicatively linked to the integration system 105 . For example, the remote access device can be a physician's home computer linked via the Internet to the integration system 105 . In another example, the remote access device can be a data tablet wirelessly connected to the integration system 105 . Additionally, the remote access device 130 can be a warning mechanism, such as an auditory or visual alarm that can be triggered upon the receipt of a specified signal from the integration system 105 .
The research information system 135 can be an information system containing data relating to clinical research involving physiologic data. While the research information system 135 can be dedicated to a single research facility, the research information system 135 can also contain multiple different geographically separated research institutions and/or organizations. For example, the research information system 135 can be a general university system that includes multiple interconnected medical universities located within one or more countries.
FIG. 2 is a schematic representation of an integration system 200 for integrating physiologic information used in conjunction with the system of FIG. 1 . System 200 can include a bedside device 205 , a trusted network 210 , a care unit device 215 , a care network device 220 , a centralized data repository (CDR) 230 , and one or more bedside machines 235 . The bedside machines 235 , which have been previously defined in FIG. 1 , can be a sensor of physiologic data that can determine one or more parameters relating to the health of a patient. Each bedside machine can include a data port 240 . If the data port 240 is not installed at the time of manufacture, one potentially can be retrofitted for the bedside machine 235 . The data ports 240 can convey a data stream between the bedside machine 235 and the bedside device 205 . The data port 240 can include any serial or parallel connection such as FireWire, USB (Universal Serial Bus), Centronics, an infra-red port, and the like. For example, the data port 240 can be an RS-232 connector that can convey information as a serial data stream.
The bedside device 205 can be a computing device capable of managing and presenting physiologic data at a bedside location. For example, the bedside device 205 can be a computer that accesses and organizes patient data. Alternately, the bedside device can be a communication portal that reconciles data streams between local equipment and a network. Multiple bedside devices 205 can be utilized within system 200 , where each bedside device 205 can manage data for one or more patient beds. The bedside device 205 can handle a variety of different peripheral devices. These peripheral devices can include one or more bedside machines 235 , a local data store 227 and a presentation device 255 . Further, the bedside device 205 can include a data port 240 that is compatible with the data port 240 of the bedside machine 235 . The bedside device 205 can also include device drivers to convert received data streams to a format independent of any particular bedside machine 235 .
The local data store 227 can be any type of information storage device compatible with the bedside device 205 , such as magnetic, optical, and/or electronic storage devices. By storing data locally within the local data store 227 , the system 200 can provide integrated data even when network difficulties prevent the bedside device 205 from accessing the trusted network 210 . The local data store 227 can store ‘raw’ data from the bedside machine 235 , as well as data from other information sources connected to the trusted network 210 . The presentation device 255 can be any device capable of presenting data stored within the local data store 227 to a user. The presentation device 255 can include, but is not limited to, a computer monitor, a touch screen, a printer, a fax machine, and/or an audio output device. The bedside device 205 can communicate to the trusted network 210 via a network gateway 250 .
The bedside device 205 can also contain a driver for each different bedside machine 235 connected thereto. This driver can be used to translate the data stream into content that can be relayed across a network. Each driver can have knowledge of a corresponding type of bedside machine 235 . The device driver can interpret device specific protocols for data streams of the bedside machine 235 . Additionally, different drivers can be used to interpret data streams sent from different bedside machines 235 .
The trusted network 210 can be an intranet including communicatively linked caregiver computing assets. Some of the devices within the trusted network can be isolated from other communicatively linked devices using network firewalls 255 . Within the trusted network 210 , physical and logical security precautions can be taken to impede unauthorized information access. A few of the caregiver computing assets that the trusted network 210 can link include the bedside device 205 , the care unit device 215 , the care network device 220 , the CDR 230 , and one or more other networks 260 .
The care unit device 215 can be a computing device that maintains information on a unit level for a health institution. For example, The care unit device 215 can include, bus is not limited to, personnel information for various shifts, bed availability information, an inventory of bedside machines, operating room schedules for a given care unit, and contact information for patients, physicians, and staff. In one embodiment, the care unit device 215 can include physiologic information derived from various bedside devices 205 within a care unit. For example, the care unit device 215 can be located within a unit nursing station and can include summary information for all bedside machines 235 in use within the care unit. Further, the care unit device 215 can provide warnings whenever parameters for a given bedside device exceed predetermined limits. The care unit device 215 can also present reminder information detailing when particular patients require assistance, such as needing fluids replaced, pills dispensed, and/or need sanitary assistance.
The care network device 220 can be the computing device that maintains information on the care giving network level, therein providing inter-unit coordination. The care network device 220 can assure that when patients are transferred from one bedspace or care unit to another, all treatment information is properly transferred. For example, if a patient is moved from one bed to another, the care network device 220 can assure the appropriate information is presented within the bedside device 205 associated with the new bed. Additionally, the care network device 220 can display warnings when the same patient is simultaneously assigned to multiple beds or when a current patient that has not been discharged is not assigned to any bed. Moreover, the care network device 220 can assist in patient management for a hospital, hospital system, or health care network. The care network device 220 can also include summary data for the various units that comprise a heath care network.
The CDR 230 can perform data reconciliation between two or more diverse sources. For example, the CDR 230 can synchronize patient data from a laboratory database with similar information contained within a database of a hospital information system. In another example, the CDR 230 can convert information presented in a machine specific format from one of the bedside machines 235 into a standardized schema. Patient information received by the CDR 230 can be converted to adhere to defined data standards and stored in a machine independent data store 275 .
In order to perform these data conversions, tables that cross-reference machine or database specific data to standardized data can be stored within a machine specific data store 270 . Each supported data source, such as a particular bedside machine 235 , can have appropriate cross reference tables for data conversion stored within the machine specific data store 270 . For example, one bedside machine 235 can store pulse rate as a floating-point variable called RATE, while the data standard can record pulse rate as an integer variable called PULSE. In this example, data stored within the machine specific data store 270 can detail that RATE equals PULSE. The CDR 230 can also convert the content within the variables from a floating-point value to an integer. Using the machine specific data store 270 information can be conveyed to and from various sources within the trusted network 210 without concern for data formatting peculiarities.
It should be noted that the CDR 230 can perform real-time and/or near-real-time data conversions. Accordingly, information from the bedside machine 235 can be converted by the CDR 230 to a data standard. The standardized data can be conveyed to the bedside device 205 for display. Performance considerations necessary for real-time conversions can require some of the converting functions normally carried out within the CDR 230 to be performed with the bedside device 205 . In such an instance, functions and/or conversion information can be sent to the bedside device 205 from the CDR 230 . In one embodiment, each bedside machine 235 can perform the functionality attributed to the CDR 230 . In such an embodiment, the bedside machine 235 can monitor and translate present physiologic data from multiple ones of the bedside machines 235 without the assistance of external networked elements.
The trusted network 210 can be communicatively linked to network 260 through gateway 255 . Gateway 255 can provide security measures, such as passwords and encryption algorithms, to assure that only authorized parties can access the trusted network 210 . Various sources that can access the trusted network 210 can include, but are not limited to, a laboratory 270 , a hospital information system 272 , a pharmacy information system 274 , a researcher 276 or clinical research facility, a doctor 278 , and an administrator 280 .
In operation, a patient can be monitored by the bedside machine 235 that includes the data port 240 . A data stream, such as a byte-level data stream, can be sent from the bedside machine 235 to the bedside device 205 . When the data stream is conveyed at the byte-level, the data port 240 can function as an interface between data terminal equipment (the bedside machine 235 ) and data communication equipment (the bedside device 205 ), which can employ binary data interchange to convey information. A device driver within the bedside device 205 can facilitate communications with the bedside machine 235 .
For example, the bedside machine 235 can be used for monitoring blood pressure. Such a machine can generate a data stream having discrete 20 byte segments, where the first 4 bytes in each byte segment identify the machine, the next 6 bytes contain a timing parameter, the next 5 bytes a systolic value, and the final 5 bytes a diastolic value. The device driver for the bedside machine 235 can correctly interpret the segments data stream for the machine. Notably, a different manufacturer of a different bedside machine 235 for blood pressure monitoring can segment a data stream into 30-byte segments. The different bedside machine 235 can have a different driver associated with it. Both blood pressure machines described can be alternatively used within the system 200 .
Once data stream information has been properly segmented, the segmented information can be relayed from the bedside device 205 to the trusted network 210 via the gateway 250 . Then, the data from the bedside machine 240 can be converted into a standard format by the CDR 230 . The converted information can be copied into the machine independent data store 275 and transferred to the bedside device 205 . Information can also be provided by other data sources such as the laboratory 270 , the hospital information system 272 , and the pharmacy 274 . The data from other data sources can be integrated within the bedside device 205 . Further integrated information can be accessed externally from remote computing devices. For example, a doctor on-call can access the bedside device 205 information via the Internet, even when that doctor is offsite. This ability can help provide correct and rapid responses to changes in patient health as well as relieve doctors of needless visits. Thus, better care can be provided at less cost to the patient.
FIG. 3 is an exemplary graphical user interface (GUI) 300 for a bedside device of FIG. 2 . The GUI 300 can include a patient overview section 305 , an application selection section 310 , a content selection section 315 , a content selection 320 , and an input section 325 . The patient overview section 305 can include general patient information such as date, unit, name, bed, height, weight, sex, and a patient identifier. In particular embodiments, additional patient background information, such as patient history, can be accessed by clicking an appropriate button located within this section. The information within the patient overview section 305 can be derived from a number of sources including a hospital information system.
The application selection section 310 can allow for the selection of one or more integrated applications. The application selection section 310 can include, but is not limited to, applications for bedside machines, laboratories, trends, reports, and patient flowsheets. In one embodiment, the selection made within the application selection section 310 can be linked to the content selection section 315 . In such an embodiment, a selection made within the application selection section 310 can cause different options to appear within the content selection section 315 .
In another embodiment, a selection within the application selection section 310 can open a view within which the selected application can appear. This window can be an emulation window showing the content of a networked application. For example, the selection of the machine button within the application selection section 315 can cause a window to appear emulating the screen of a selected machine, such as an infusion pump or a pulse oximeter. Such an emulation screen can be useful for physicians, who are familiar with standard machine readouts, to view patient data, whether the physician is at the bedside or accessing the system from a remote location.
The content selection section 315 can allow one or more selections to be made which determine the content displayed within the content section 320 . The content selection section can display a flowsheet interval, such as 15 minutes or another predetermined or selectable time interval, which represents the time frame in which new flowsheet data should be gathered. The flowsheet interval can be selected by the treating physician depending on the needs of the patient.
The content section 320 is the main section of the GUI 300 and can display selected patient information. In GUI 300 , the content section 320 presents patient information including, but not limited to, patient identifier, last name, blood type, birth date, unit, mother's name, gender, room, and bed. The patent information displayed within the content section 320 can vary depending on patient age, type, and care unit. For example, the mother's name and blood type can appear within the content information section 320 whenever the patient is a newborn.
The input section 325 can be available whenever the GUI 300 appears within systems with touch screen capabilities or other input means, such as a printing device. Thus, although peripheral keyboards can be used, such devices are not necessary for operation. Alternately, the GUI 300 can appear within a personal data assistant (PDA) communicatively linked to a bedside device. Since a bedside device will commonly be located within a patient's vicinity, touch screens, such as the one depicted in the input section 325 , represent one minimally intrusive way to provide an input means for the bedside device. It should be noted that any input device, such as a stylus, an external keyboard, and/or a microphone for speech input, can be included within the invention.
FIG. 4 is an exemplary GUI 400 showing flowsheet data for patient fluids using the system of FIG. 2 . The GUI 400 utilizes the same conventions described within FIG. 3 and can, but need not, be used in conjunction with the GUI shown in FIG. 3 . The content section 420 of GUI 400 displays summary data for fluids received by a patient. Additionally, clinician notes (not shown), such as particular symptoms to visually check when performing rounds can be included as well. The fluid settings displayed within the fluid summary can be manually entered by treating staff and/or can be automatically entered via a direct communication connection with a fluid controlling bedside machine.
In one embodiment, the GUI 400 can be integrated with a hospital inventory system where patient fluids can contain a bar code. Before a patient is infused with a fluid, the selected fluid can be scanned. If the annotations associated with the scanned fluid do not match physician annotations for treatment, a warning message (not shown) can be displayed by GUI 400 . Further, once the fluid is scanned, information within GUI 400 , as well as other system information, can be automatically updated. Such an embodiment demonstrates one of many potential advantages and automatic safeguards that can be implemented within a patient care facility where bedside patient care data is integrated among various networked information systems.
FIG. 5 is an exemplary GUI 500 showing data for multiple bedside machines using the system of FIG. 2 . The GUI 500 demonstrates that data from more than one bedside machine can be simultaneously displayed. Available beside machines associated with a particular bedside device can appear within the content selection section 515 . Check boxes, or other selection criteria, can be provided so that system users can determine what information should appear within the content section 520 . If multiple ones of the same bedside machine type are used for a given patient, such as Flo-Gard 1 and Flo-Gard 2 (a Flo-Gard bedside machine being available through Baxter Healthcare Corporation of Deerfield, Ill.), data from both machines can be displayed.
The data displayed within GUI 500 can represent a situation where multiple bedside machines have been connected to a particular patient at different times. For example, in one embodiment, Flo-Gard 1 , Flo-Gard 2 , and Colleague IP were used on a particular patient that has received fluids. Since the invention can reconcile data differences among differing bedside machines, the same data elements for different machines can be presented within GUI 500 . Additionally, the data from the different bedside machines can be easily merged together. Accordingly, although fluids were delivered and measured by three different bedside machines, a single composite graph or chart (not shown) for the patient's fluid intake and status can be automatically created and displayed.
FIG. 6 is an exemplary GUI 600 for configuring a flowsheet display using the system of FIG. 2 . GUI 600 illustrates that data from various data collection sources, such as the lab, bedside machines, and user entered flowsheets, data elements can be configured for the needs of a particular patient and/or treating physician. In GUI 600 , each unit can have different presentation and data requirements associated with it. Once a unit is selected within selection box 605 , a number of defaults can be automatically displayed in defined data box 610 . For example, the selection of NICU for unit can cause the display data to contain elements for birth length, fluid output, urine output, and the like. The flowsheet setup can also have an associated flowsheet interval. A default flow sheet interface can be determined based on the bedside machines connected to a particular patient.
FIG. 7 is an exemplary GUI 700 for configuring a trend display using the system of FIG. 2 . The GUI 700 allows a user to configure what trends the system should monitor as well as the trends that should be displayed. Different users using different computing devices can be presented with different trend options. For example, a treating physician using a bedside device can be presented with trends for particular patients in scroll box 705 . Additionally, a physician can be presented with trends relating to variables within bedside machines that monitor treated patients. For example, trends related to detected physiologic data from different sources can be determined, such as a relationship between a value recorded by a pulse oximeter and a value from a flowmeter.
In another example, a care unit administrator using a care unit device can be presented with trends showing the volume of patients cared for by month and corresponding hardware resource requirements. In yet another example, a hospital facilities administrator can use a care network device to determine maintenance verse operational time for a particular type of bedside machine. Further charts comparing different types of bedside machines can be displayed along with any annotations made by physicians, staff, and maintenance concerning that machine type. Trends and charts from any communicatively connected source can be analyzed by the system.
FIG. 8 is an exemplary GUI 800 showing trends using the system of FIG. 2 . The GUI 800 displays trends for a particular machine type, the Babylog 8000 . Values can be selected within the content selection section 805 for display. In the example shown in GUI 800 , the peak inspiratory pressure (PIP), continuous positive airway pressure (CPAP), and inspiratory and expiratory times (IE ratio) have been selected for the Babylog 8000 . Responsively, graphs showing the selected values verses time can be displayed within the content section 810 . Each graph can be displayed according to a selected time frame, such as by the hour, shift, day, week, month, or any other time period. In particular embodiments, treating physicians can set conditions upon monitored trends that cause a message to be responsively displayed upon the occurrence of that condition. For example, if a particular patient's temperature rises above a defined reading, such as 103 degrees Fahrenheit, for longer than a minute, a warning can be generated within the appropriate bedside device and the appropriate care unit device. This ability to add algorithmically determined conditions can supplement warnings generated by particular bedside machines.
It should be appreciated that the GUIs of FIGS. 3 through 8 can be displayed on a variety of different computing devices. Each of these devices can be used conjunctively or alternatively with the various computing devices described within FIG. 2 . Further, the computing devices shown in FIG. 2 can use wired or wireless connections for exchanging information between the various computing devices of the system.
For example, in one embodiment the GUIs can be presented within a personal data assistant (PDA) carried by a treating physician. The PDA can contain a networking component, such as a Bluetooth attachment that can convey signals to and from bedside computing devices. The closest bedside device that is within range of the PDA, typically 30 feet, can transmit information to the bedside device. Thus, any comments and/or annotations that the physician made within his/her PDA concerning the patient can be automatically transferred to the bedside device. Additionally, a physician making rounds can retrieve updated information concerning his/her patients to be fully examined at a later time, such as when the physician is called concerning dispositional instructions for a given patient.
In another embodiment, an identification chip can be implanted within a patient's ID bracelet. This identification chip can assure that physician's have the appropriate patient information. For example, if a patient is rushed into an operating room for emergency care, the identification chip can be read and the patient's information displayed within a bedside device of the operating room. Consequently, the invention can be used within a pervasive computing environment to assure that patient data is not confused and that the correct information is always available to treating physicians within a dynamic health care environment.
The various GUIs disclosed herein are shown for purposes of illustration only. Accordingly, the present invention is not limited by the particular GUI or data entry mechanisms contained within views of the GUI. Rather, those skilled in the art will recognize that any of a variety of different GUI types and arrangements of data entry, fields, selectors, and controls can be used to access system 200 . Further, the computing devices depicted herein can be functionally and/or physically implemented with other computing devices and the invention should not be limited by the particular exemplary configuration shown.
The present invention can be realized in hardware, software, or a combination of hardware and software. The present invention can be realized in a centralized fashion in one computer system or in a distributed fashion where different elements are spread across several interconnected computer systems. Any kind of computer system or other apparatus adapted for carrying out the methods described herein is suited. A typical combination of hardware and software can be a general-purpose computer system with a computer program that, when being loaded and executed, controls the computer system such that it carries out the methods described herein.
The present invention also can be embedded in a computer program product, which comprises all the features enabling the implementation of the methods described herein, and which when loaded in a computer system is able to carry out these methods. Computer program in the present context means any expression, in any language, code or notation, of a set of instructions intended to cause a system having an information processing capability to perform a particular function either directly or after either or both of the following: a) conversion to another language, code or notation; b) reproduction in a different material form.
This invention can be embodied in other forms without departing from the spirit or essential attributes thereof. Accordingly, reference should be made to the following claims, rather than to the foregoing specification, as indicating the scope of the invention.
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A method of integrating physiologic data including receiving physiologic treatment data from at least two bedside machines and converting the physiologic treatment data into a machine independent format. The physiologic treatment data can be presented in perceptual real-time. For example, physiologic treatment data from multiple sources can be simultaneously presented within a single graphical user interface. The graphical user interface can be interactive so that displayed graphs can be replotted and timelines revised responsive to user input, such as a point-and-drag motion.
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BACKGROUND OF THE INVENTION
The present invention concerns a catalyst system for alkylating alkyl aromatics, e.g. for alkylating toluene, a procedure for preparing the catalyst system, and a procedure for carrying out the alkylation of the alkyl aromatics, i.e. alkylating toluene.
Alkaline metal catalysts well-suited for side-chain alkylation of alkyl aromatics with olefins are known in the art, in which the metallic sodium or potassium has been dispersed onto the surface of an inorganic or graphite carrier. For instance, in the Neste Finnish Patent Application No. 865,362, a catalyst system is disclosed which contains metallic sodium on a K 2 CO 3 carrier. A catalyst is known from British Patent No. 1,269,280, which is produced by dispersing sodium and/or lithium on a nonaqueous potassium compound. Additionally, reference is made to the Neste Finnish Patent Application No. 865,363, in which the catalyst system used contains metallic sodium dispersed thermally from a sodium-containing compound onto a surface of a solid K 2 CO 3 .
However, drawbacks of such catalysts include cumbersome manufacturing and processing of the catalysts, a relatively low activity at high temperatures, and rapid decrease of activity as a consequence of the catalysts becoming tarred and coked.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to improve over the above-noted catalytic systems of the prior art, eliminating the drawbacks noted above with respect thereto.
It is also an object of the present invention to improve the ease with which an appropriate catalyst system for alkylating alkyl aromatics with olefins, can be prepared.
It is another object of the present invention to provide a catalyst for alkylating of alkyl aromatics with olefins, having improved activity.
These and other objects are attained by the present invention which is directed to a catalyst for alkylating alkyl aromatics with olefins, the catalyst comprising sodium oxide on a potassium carbonate carrier. The present invention is also directed to a method for producing such a catalyst, which comprises the step of mixing the sodium oxide and the potassium carbonate. The present invention is furthermore directed to a method for the alkylation of alkyl aromatics with olefins, comprising the steps of carrying out the alkylation in the presence of a catalyst system comprising sodium oxide on a potassium carbonate carrier.
The catalyst of the present invention represents improvement in comparison with the above-noted catalysts of the prior art, in that the starting materials are easier to process and yet the catalyst is as active as the alkali metal catalyst.
The catalyst system of the present invention contains sodium oxide (Na 2 O) on a potassium carbonate (K 2 CO 3 ) carrier. The sodium oxide concentration is preferably about 10 to 70%, more preferably about 40 to 60%.
The procedure for producing the catalyst system of the present invention is characterized in that the catalyst system is manufactured by mixing sodium oxide (Na 2 O) and potassium carbonate (K 2 CO 3 ). Preferably, the quantity of sodium is about 10 to 70%, more preferably about 40 to 60%, in the mixing thereof with the potassium carbonate.
The procedure for alkylating toluene is characterized by the catalyst system utilized for carrying out this alkylation being composed of sodium oxide (Na 2 O) on a potassium carbonate (K 2 CO 3 ) carrier. Preferably, the sodium oxide concentration of the catalyst system is about 10 to 70%, more preferably about 40 to 60%.
The production of the catalyst of the present invention is carried out in a simple manner by mixing sodium oxide in potassium carbonate, and by heating the mixture. The heating may take place at 100° to 400° C. temperature, but most advantageous and rapidly the heating takes place at 260° to 280° C. temperature, with a preferable heating period being about 0.5 to 1 hour. The heating is carried out advantageously, but not necessarily, in a vacuum.
It is surprising that the catalyst of the present invention may be active, since neither sodium oxide nor potassium carbonate alone displays any activity, and no chemical reactions take place between the potassium carbonate and the sodium oxide, as evidenced by the fact that in the X-ray diffraction analysis of the completed catalysts, the intended phases, i.e., sodium oxide and potassium carbonate, were identified.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will now be described in greater detail below, with reference to preferred embodiments thereof illustrated in the accompanying drawings, in which
FIG. 1 is a graph of alkylating conversion as a function of catalyst concentration in accordance with the present invention, and
FIG. 2 is a graph of catalyst activity as a function of catalyst concentration in accordance with thee present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The catalysts of the present invention were tested with propylene by side-chain-alkylating toluene.
The alkylating reaction can be illustrated with the following reaction equation: ##STR1##
The main product produced in the reaction is isobutyl benzene; n-butyl benzene and a dimerization product of propylene, 4-methyl-1-pentene, are produced as byproducts as a result of by-reactions.
The tests were carried out in a 1 dm 3 autoclave and in a continuous-action microreactor.
After the reaction, the gas and liquid phases were analyzed by gas-chromatography.
The invention is described in detail below with the aid of a catalyst production example and an alkylating example. However, the present invention is not intended to be restricted to the details thereof.
CATALYST PRODUCTION
The catalyst was produced in a 1 dm 3 Parr steel reactor at 270° C. temperature and in a vacuum. The desired amounts of sodium oxide and potassium carbonate were weighed into the reactor, which was closed, and the vacuum was established. The mixture was heated to 260° to 280° C., at which it was maintained for 0.5 to 1.0 h.
Seven catalysts were prepared, with the sodium content varying from 0 to 100 percent by weight.
ANALYZING CATALYSTS
The completed catalysts were dark grey or brownish in color. When producing catalyst containing sodium oxide of 14 to 90% by weight, a metallic phase could be observed on the walls of the reactor. Of the completed catalysts, a catalyst containing 40% by weight sodium oxide was analyzed using an X-ray diffraction metric method (XRD). The phases identified in the diffraction analysis that were present in the catalyst, were sodium oxide, potassium carbonate, and probably metallic sodium. The sodium oxide had large crystals and its concentration was high. Potassium carbonate had either small crystals or it was coated by sodium oxide because the peaks were low in intensity and wide.
TESTING THE CATALYSTS
The catalysts were tested by side-chain alkylating toluene with propylene. The tests were carried out in a 1 dm 3 Parr autoclave and in a continuous-action microreactor.
TESTS IN A CHARGE REACTOR
The following were selected for the reaction conditions: reaction time t =19 h; reaction temperature T =175° C.; toluene/propylene molar ratio n(T)n(P) =0.7; catalyst mass m =23.0g.
The catalyst was loaded into the reactor under nitrogen atmosphere. The reactor was closed and vacuum was produced. Toluene was conducted into the reactor with the aid of the vacuum prevailing in the reactor through a valve in the reactor cover. Propylene was supplied in liquid form into the reactor.
After the reaction (175° C., 19 h), the gas and liquid phases were analyzed by gas-chromatography.
RESULT OF CHARGE EXPERIMENTS
Isobutyl benzene (IBB) was obtained as the main product in the reaction. The product mixture also contained n-butyl benzene (NBB), 4-methyl-1-pentene (4M1P) as a dimerization product of the propylene, isomerization products of the 4M1P, and various hexene isomers, as a result of the by-reactions.
A summary of the results of the test runs is presented in Table 1. From the composition of the product, the conversions of the starting materials into products, the formation selectivities of various product components, and the activity of the catalyst regarding the IBB production were calculated. The conversion of the toluene and propylene into products as a function of the sodium oxide concentration contained in the catalyst, is presented in FIG. 1. The activity of the catalyst in grams of IBB per catalyst gram g IBB/ (g cat.)), is presented in FIG. 2.
TABLE 1______________________________________Summary of the test runs with the Na.sub.2 O/K.sub.2 CO.sub.3 catalyst. IBB/ Cat. Con- NBB act.Catal. versions Selectivities ratio gNa.sub.2 O tol. prop. IBB NBB 4MIP ISOM. mol/ IBB/g% by w. % % % % % % mol cat.______________________________________ 0 0.0 0.0 0.0 0.0 0.0 0.0 -- 0.014 13.4 20.7 68.4 6.2 8.4 4.0 11 1.820 46.2 64.0 66.4 7.4 4.8 8.0 9 4.840 58.4 63.5 71.7 7.5 4.7 8.7 10 6.060 64.8 73.8 70.9 7.1 3.5 9.1 10 6.690 26.5 43.7 72.8 8.3 6.6 7.7 9 3.3100 0.0 0.0 0.0 0.0 0.0 0.0 -- 0.0______________________________________ IBB = isobutyl benzene, NBB = nbutyl benzene, 4MIP = 4methyl-1-pentene, ISOM = isomerization products of 4MIP
It is observed from Table 1 and FIGS. 1 and 2, that the conversion as well as the activity of the starting materials are best with a catalyst in which the sodium concentration is 60% by weight. However, the results are not significantly poorer with catalysts containing sodium oxide of 20 or 40% by weight.
When the Na 2 O/K 2 CO 3 catalyst is compared with a catalyst which is prepared from a pure alkali metal and alkaline metal carbonate (6% Na/K 2 CO 3 ), the results are remarkably better with a 20, 40 and 60% oxide catalyst, in comparing the conversions and the activities of the catalysts. With the Na/K 2 CO 3 catalyst in test runs carried out under the same conditions, the toluene conversion is 30%, the propylene conversion is 42%, and the activity of the catalyst is 4 to 5 g IBB/(g cat), while the conversions with catalysts containing 20 to 60% by weight sodium oxide are 46 to 65% in toluene conversion, 64 to 74% in propylene conversion, and the activity of the catalyst is 5 to 7 g IBB/(g cat).
Additionally, it was observed that the oxide catalysts becomes readily activated, and no induction time was noted in the reaction. In other words, the pressure in the reaction started to fall immediately after the temperature had risen to 175° C. The starting of the reaction took about one hour with the alkaline metal catalyst instead.
A significant difference between the alkaline metal catalyst and the oxide catalyst is the high isomerization efficiency of the 4M1P in the oxide catalyst. The formation selectivity of the isomerization products of the 4M1P with the oxide catalysts is about doubled as compared with the alkaline metal catalyst. However, the isomerization may be reduced by lowering the reaction temperature and shortening the reaction time.
CONTINUOUS-ACTION REACTOR
A 40% Na 2 O/K 2 CO 3 catalyst was selected for a continuous-action microreactor run. The parameters of the run were as follows: toluene feed about 9 g/h; propylene feed about 20 g/h; reactor temperature 170° C. and reactor pressure 90 bar. 26 g of the catalyst was loaded.
The Na 2 O/K 2 CO 3 catalyst appeared to be especially suitable for producing isobutyl benzene in a continuous-action reactor because its tar formation (products heavier than NBB) is especially low. The proportion of tars is not increased either, with temperature increase and catalyst ageing. Although the Na 2 O/K 2 CO 3 catalyst in rather finely powdered, no pressure losses can be observed in the reactor because the tarring of the catalyst is non-existent. Therefore, the temperature of the reactor can be raised up to 200° C. A drawback in the Na 2 O/K 2 CO 3 catalyst, is its tendency to produce 4-methyl-2-pentene as a main dimerization product. Such isomerization tendency is strongly dependent on the temperature. The lowering of the temperature to 150° C. returns the isomerization close to the isomerization ratio characteristic of the Na/K 2 CO 3 catalyst.
TABLE 3______________________________________Microreactor run with 40% Na.sub.2 O/K.sub.2 CO.sub.3 catalyst Selectivities (%) ProductonRun time Tol. conv. other h/g cat.(h) (%) 4MlP hex. IBB NBB 4MlP IBB______________________________________ 73 48.6 32.6 11.0 49.0 6.6 0.15 0.23162 32.8 23.0 8.0 57.1 5.2 0.07 0.16260 10.0 17.8 7.3 63.9 5.5 0.05 0.16______________________________________
The preceding description of the present invention is merely exemplary, and is not intended to limit the scope thereof in any way.
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The present invention concerns a catalyst for alkylation of alkyl aromatics with olefins, i.e. alkylating toluene, a procedure for the production of the catalyst, and a procedure for carrying out the alkylating of the toluene. The catalyst system contains sodium oxide (Na 2 O) on a potassium carbonate (K 2 CO 3 ) carrier, preferably at about 10 to 70%.
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CLAIM OF PRIORITY
This application claims the benefit of priority of U.S. Provisional Patent Application Ser. No. 62/237,948, filed on Oct. 6, 2015.
FIELD OF THE INVENTION
The present invention relates to the detection and location of water leakage in structures, and in particular to computer controlled leakage detection and location systems for roofs and roof flashing.
BACKGROUND
Roof and waterproofing membranes and linings have long been used to protect buildings, to contain water in ponds and decorative water features, to prevent leaching of contaminants from landfills, and for other purposes. While these membranes have utility, leakage through the membranes is an ongoing problem. The efforts to contain and locate leakage have resulted in the rise of specialized consultants, air and vacuum testable membranes, and, in recent history, electrical testing methods that not only determine if a leak is present in a membrane system, but where the leak is located.
Leakage in existing roofs is a particular problem, especially when the roof has a nonconductive element at the bottom of the roofing envelope next to the deck, such as a vapor barrier or a secondary roofing membrane. In these cases, water leaking into the roofing envelope can saturate the insulation and other elements in the envelope without actually leaking into the building because the lowermost membrane acts as a barrier to the water. In time, water might run into the building via penetrations, such as vent stacks, curbs for mechanical equipment, conduits, etc., through the roofing envelope and be visible from underneath. By this time, corrective action may be as extensive as cutting cores in the roofing envelope to determine the extent of water damage; removing a large portion of the roof; performing infrared or other tests to indicate the current status of the roofing envelope; etc.
Additionally, when the roofing envelope becomes saturated with water, a portion of the planned energy efficiency from the roofing envelope is lost. The building structure may also experience the corrosive effects of water, therefore compromising its penetrations. Unbeknownst to anyone, this process is occurring in thousands of roofs across North America and, indeed, in the built environment anywhere in the world.
There are methods that have been developed to address the above described problems including manual methods, such as capacitance testing, infrared scanning, and moisture probing. In addition, there are automatic systems driven by computers with sensors built into or retrofitted into the non-conductive insulation and other non-conductive materials which comprise the roofing envelope.
One known method of placing such an automatic system into a non-conductive envelope is to install relative humidity sensors in the roofing envelope, where the sensors measure humidity and temperature. An array of such sensors can give a representation of moisture conditions in a roofing envelope. Such a system is provided by Progeo GmbH of Germany and other vendors, and these systems have been used on projects in the United States. Such systems are limited in that the sensors require a certain amount of free air around them in order to determine the ambient moisture content of any part of the roofing envelope, and each sensor is only one point, measuring the relative humidity of a very small area around its location. Further, there is no guarantee that any air will circulate in the roofing envelope, and if the free flow of air is cut off, especially given the impermeable nature of closed-cell insulations in today's roofing envelopes, the sensors will not be able to sense variations in moisture, but only temperature changes.
The computer attached to such a system is given the task of correlating all the data received from the sensors in these distinct, small areas, and of producing a table, graph, or other graphic based on the extrapolations of these data. In order for the data to be at all relevant, the computer must make a correlation reading from a sensor located on the outside of the roofing envelope so that it can compare trends in relative humidity on the outside of the roof to the trends being determined by date from the sensors within the roofing envelope. The results are skewed when the temperature changes within the roofing envelope, outside the roofing envelope, or both. The skew is particularly pronounced when temperature changes precipitously, and a certain amount of time is required, sometimes days or weeks, before the system can stabilize enough to produce relevant data again. Even so, relevant data can only be surmised, as the circulation of free air in the roofing envelope cannot be adequately determined, especially across the entire expanse of the envelope. If these systems are retrofitted using tubes inserted into holes cut into the roofing envelope, the temperature sensed in the tubes is different from the actual temperature in the roofing envelope as a whole, and incorrect temperature and the contingent relative humidity measurements are inaccurate, causing false leakage alerts. Further, in order to make such a system more responsive or accurate, sensors must be deployed much closer to one another so the computer will have a greater number of points from which to draw and extrapolate data, driving the cost of the system up. In summary, such systems have significant drawbacks. In addition, the inventor has developed several automatic systems, such as those disclosed in U.S. Pat. Nos. 8,566,051 and 9,341,540 and co-pending U.S. patent application Ser. Nos. 13/442,586, 14/061,480, and 14/107,694, each of which is hereby incorporated by reference.
Another known automatic system requires a grid of hydrophobic cables, the cross-over points of which, when wetted from water flowing through the roofing membrane, make a closed circuit that identifies which portion of the grid is wet and allows location of the leakage through the membrane. This system requires water to make its way to the cross-over points to trigger an alarm and a significant flooding of a portion of the roofing envelope might occur before an alarm is tripped. Such a system is sold under the trademark DETEC.
All of the above named systems require considerable effort on the part of the contractor installing the roofing or waterproofing membrane, as the sensors must be placed within the roofing envelope as the envelope is being constructed, requiring a tremendous amount of coordination between the roofing contractor and the person or firm responsible for installing the sensors. This is because roofing on any project is subject to fits and starts because weather so drastically affects the construction schedule of the roofing envelope.
The most efficient way to build a leak detection system for membrane roofing or waterproofing, therefore, is to have the roofer install the simplest element possible of the leak detection system. In other words, if any part of the leak detection system is performed by the roofing contractor, it will be elements of the system within the roofing envelope, i.e. under the roofing or waterproofing membrane, that are elements that the roofing contractor may already customarily install. In this way, the roofing contractor will not have to deal with any more detail than is necessary to complete the roofing envelope. Thus, a conductive mesh or mat may be placed, just like a roll of roofing, underneath the membrane and within the roofing envelope. The conductive mesh or mat may be made from metal, glass, or plastic and is commonly available in various forms. This involves actions the roofer uses every day a roof is installed. This mesh may be further zoned by electrically isolating a zone or area of the mesh from other zones or areas of the mesh by simply adding a non-conductive strip of roofing or other non-conductive material. Applying strips of membrane or other sheet materials is also something a roofer does on a regular basis.
The sensors are then placed on top of the finished roofing by experienced installers of the leak detection system. This requires minimal involvement from the roofer or other trades, thus assuring that the leak detection system is properly positioned and that the membrane is not penetrated unnecessarily.
This division of labor between general roofing contractors and specialized leak detection system installers provides several advantages: The roofer does not need to be present when the sensors are installed; The sensors and wires may be installed after the roof is finished so that timing of the placement of the system can be coordinated with the last trades working on or around the roof; The sensors may be checked just before application of the overburden, if any.
FIGS. 1A-1C depict a prior art system as described above. The disadvantage of placing sensors on top of the roof is accurately reading the sensors 1 . The sensors 1 are placed on top of the roofing membrane 14 and surrounded by a boundary cable (not shown) placed in a loop around the sensors 1 . Roofing membrane 14 is disposed on top of a conductive mesh or medium 4 . The conductive mesh or medium 4 is placed under the membrane 14 and acts to attract the signal generated by a signal generator (not shown). The system also includes power supply 5 . Power supply 5 references sensors 1 to the return side and powers mesh 4 . As power supply 5 is common to each, if a leak 6 occurs in the membrane 14 , the mesh 4 will complete the circuit and a change in the current will occur and be detected by the sensors 1 . The power supply 5 for this system is contained in the computer driven module (not shown) to which the boundary cable and the sensors 1 are connected.
If all goes smoothly, as the sensors 1 and the mesh 4 are connected to the same reference, the sensor 1 that is nearest the breach 6 will read a lower voltage. The location of the breach 6 in the membrane 14 will be able to be triangulated based on the varying voltages detected by the sensors 1 disposed at different distances from the breach 6 . This rarely occurs in real-world roofing or waterproofing, however, as there are elements such as stray electrical influences that contribute current to the surface of the roofing or waterproofing membrane 14 , either on the bare membrane or in any type of overburden that might later be applied to the surface of the membrane 14 . Examples of stray electrical influences 7 include lightning arrestor cables, conduits and vents, lighting on the roof, weather stations on the roof, power sources for devices such as lights and weather stations, anything with a power source, or anything with a transformer. It is known that these stray electrical signals 7 may compromise the discovery of leakage events or locations of leakage 6 . Such stray signals 7 may be misinterpreted unless the signal from the leak detection system that generates the readings to locate an actual leak 6 is strong enough to be accurately read despite conflicting or stray signals from other, non-leak detection related elements 7 , or is in some other way able to be identified as the real signal.
FIG. 1A is a top down diagram of the system with leak 6 and stray electrical influence 7 . FIG. 1C is a side diagram of the same. FIG. 1B is a potential graph, showing the potential measured by various sensors 1 mapped against their location on membrane 14 . The solid line 8 shows a graph of potential near actual leak 6 . The dashed line 9 shows a graph of potential near stray electrical influence 7 . As solid line 8 and dashed line 9 are very similar in both shape and amplitude, it would be very difficult to distinguish which is an actual leak and which is not. In other words, the signal from the leak 6 became contaminated by the stray signal 7 and, instead of lower voltage being read only at sensors 1 near the leak source 6 , the voltage rises and falls in more than one area. A contour map of this situation, showing the voltage isopleth, would resemble an area with hills and valleys. FIG. 1B is a two-dimensional example, or cross section of such a map. These hills and valleys make isolating the location of the actual leak 6 extremely difficult, if not impossible.
It is possible to isolate the leak 6 manually, using an electrical balance in a process called ‘vector mapping’, in which two poles, one held in each hand, are connected to a balanced electrical meter so that minute changes in voltage are detected, and the needle of the meter swings toward the side that has a lower voltage. This process can easily lead a trained technician to the leak 6 as long as the technician accounts for any stray signals 7 as he or she is working the method. This is in part because the poles are held only a small distance apart, usually less than 4 feet, so compensation for stray signals 7 can be accomplished by trial and error, i.e. by moving the poles on different axes.
In an effort to eliminate the need for such manual testing, it would be possible to construct an automatic real-time leak detection that has a distance between sensors of less than 4 feet. However, it is not practical to build such tight systems in reality and further, the axis of any chain of sensors cannot be changed once the sensors are secured to the membrane.
Another element that limits the effectiveness of reading sensors 1 on top of the membrane 14 is the weather, which provides wetter and drier periods. Such weather variations may skew the readings to some extent, and because the source of the current is the boundary cable located on the perimeter of the test area, the boundary cable must be wet in order to transmit the current to the sensors in the test field. Further, any discontinuance of moisture on the surface of the membrane will affect the readings of the sensors 1 if the discontinuity of the moisture blocks the signal from the boundary cable.
It is a known fact that the overburden that covers a membrane system might allow water to flow to the membrane in some places, but not in others, resulting in an uneven distribution of water at the membrane surface. It is further known that the surface upon which the membrane system is applied can be uneven, resulting in areas of water accumulation known as ponding. Both of these conditions may change the signature of the signal generated by a boundary cable and skew the interpretation of the data acquired from manual and automatic leak location systems. If the membrane is bare, these conditions may be accommodated. After application of the overburden, however, these conditions may not be verified from the surface of the overburden that has variable areas of dry or wet and conducting or not conducting. Determining leakage from the top of the overburden or from the sensors in a system in which the boundary cable is responsible for current generation therefore becomes much more difficult.
Another problem that roofing and waterproofing systems have is that edges and penetrations account for most of the leakage in the membrane system. This is because of the amount of careful hand work required to effect the waterproofing, or flashing, of walls, vents, curbs and the like. Automatic real-time leak detection systems have struggled to determine leakage at these elements, primarily because the flashings rise and are vertical, laid against a curb, wall or stack, or the flashings are flat flanges, welded to the flat of the membrane. There was no way until the present invention of determining when and where leakage could occur in flashings.
The present invention endeavors to overcome the limitations as discussed above.
SUMMARY OF THE INVENTION
The present invention is a system for detecting and locating leaks in roofing membranes, a method for detecting and locating leaks in roofing membranes, a system for detecting and locating leaks in roof flashing, a method for detecting and locating leaks in roof flashing, a system for detecting and locating leaks in roofing membranes and roof flashing, and a method for detecting and locating leaks in roofing membranes and roof flashing.
In its most basic form, the system for detecting and locating leaks in roofing membranes includes a conductive mesh disposed under the roofing membrane to be tested; a plurality of sensors disposed on top of the roofing membrane to be tested; at least one attractor cable; a power supply attached to the mesh, the sensors, and each of the attractor cables; and a computer in electronic communication with the power supply, the mesh, the sensors, and the attractor cables.
It is preferred that the power supply power the conductive mesh and be referenced by the sensors and the attractor cables. The system also works with reverse polarity, however, with the power supply powering the sensors and the attractor cables being referenced by the conductive mesh. Discussions herein refer to the former preferred embodiment, but it is understood that the reverse is also possible. For the avoidance of doubt, as used herein, an element is “powered by” the power supply or the power supply “powers” an element if that element is attached to the positive side of the power supply. Similarly, the power supply is “referenced by” an element or an element “references” the power supply if that element is attached to the negative side of the power supply. The “positive side” and “negative side” of the power supply indicate the two poles of the power supply.
The conductive mesh or mat may be any commonly used in the art and available in various forms, such as metal, glass, or plastic meshes, conductive coatings or felts, and prefabricated conductive membranes used for manual testing purposes. The mesh may be placed directly under the roofing membrane or anywhere in the cover board or insulation layer below the membrane. The conductive mesh needs to be in a position so that it will be contacted by water if the membrane should develop a leak. In addition, the mesh cannot be touching any conductive part of the building that conducts electricity to the building or to ground. The mesh is electronically connected to the computer, which will direct the power supply to energize the mesh. As used herein, the term “conductive mesh” refers to any conductive mesh or mat as described above or commonly used in the art, such as any disclosed in the inventor's patents and co-pending patent applications, which were incorporated by reference herein.
The sensors may be any commonly used in the art, such as those disclosed in the inventor's patents and co-pending patent applications. Alternatively, the sensors may be wireless or radio frequency sensors. The wireless sensors that may be used for this purpose must reference the common (-) side of the power supply so that they can read the electrical potential from the location of the sensor to the attractor cable that also references the common side of the supply. Such wireless sensors may be used only if the power supply and the attractor cables, as well as the sensors, can all reference ground or the building in common. In such a scenario, each wireless sensor would require a single wire, which could be attached anywhere to the structure of the building, including the roof deck directly below the sensor if the deck is conductive. This would provide a common reference, as the negative side of the power supply will also be attached to the common reference, allowing voltage to be read and transmitted wirelessly by the sensor unit to the receiving unit at the computer or hub. It is understood that although such a “wireless” sensor does, in fact, include a single wire, as discussed above, it is a “wireless sensor” in that the information is transmitted wirelessly. The wireless sensors may be powered by battery, solar, microwave, or other common power sources.
The attractor cables are made from any bare or partially bare (i.e. electrical insulation is removed from a portion of, or portions of the conductor) electrical conductor made from metal wire or cable, metal or conductive polymer mesh, or other materials that conduct electricity. As used herein, the term “attractor cable” includes any of these. In addition, the attractor cables may be exposed to moisture along any or all of their length or area. Although only one attractor cable may be necessary for the system, it is preferred that several attractor cables are placed around the perimeter of the area being monitored. The attractor cables are distinct and non-attached to one another, so that each direction or leg of an attractor cable is isolated from the others. The attractor cables are essentially replacing the continuous boundary loop of prior art systems with cables that are independent of one another and not connected to one another. Each is connected to the computer, however.
The power supply energizes the mesh underneath the membrane. The sensors and the attractor cables located on the top side of the membrane, when activated by the computer, reference the other side of the power supply. As discussed throughout herein, when it is said that an element is powered or energized by the power supply, then that element is attached to the positive side of the power supply. When it is said that an element is activated, it is attached to and actively referencing the negative side of the power supply.
The power supply is preferably a low voltage unit that supplies 1-60 volts of DC power and up to 10 amps, depending on the size and construction of the membrane system. This power supply may be an AC/DC converter and transformer that is attached to any line voltage available at the location of the membrane system, or it may be powered directly by battery, solar panel, etc. The computer may be any commonly used in the art, such as those described with reference to the inventor's patent and co-pending patent applications. The computer is in electronic communication with the power supply, the mesh, the sensors, and the attractor cables. The computer includes a processor, memory, and a software product for detecting and locating leaks.
The software product is stored in the memory and is executable by the processor. The software product includes instructions for energizing the mesh, activating each of the attractor cables, recording voltage readings measured by the sensors, converting recorded voltage readings into a contour map or numerical table, and reversing the polarity of the power supply. The software product also includes the various sequencing of these instructions. As contour maps are derivatives of numerical tables and are different representations of the same data, as used herein, the term “contour map” may refer to either a contour map or a numerical table.
In some embodiments, the system also includes a moisture permeable felt or other fabric disposed on top of the sensors and attractor cables. Placing such a geotextile or other permeable, moisture retaining fabric on top of the sensors can retain moisture and provide a wider and more uniform conductive layer local to the area of moisture retention and possible leakage. As used herein, the term “felt” means any moisture permeable and/or retentive felt or fabric, such as a geotextile. Further, because the sensors reference the power supply, it is preferable, but not necessary, to have such a moisture path to the attractor cables when small areas are wet and leaking, as the sensors will still read the voltage signature from the mesh if the mesh is exposed to water via a leak in the membrane.
In operation, the mesh is first energized without the attractor cables being activated. This enables the system to overlook non-problematic wet or dry conditions on different portions of the membrane that would either confuse or render the systems of prior art useless, allowing the system to analyze only areas on the roof that are wet and leaking at the same time. The attractor cables aid in defining the location of a leak on a wider area basis, and may help eliminate stray voltage signatures from other elements in the overburden. Where a local area is wet and there is a leak, however, this will still be indicated in the leak detection system as a voltage spike emanating from the sensors close to the area of leakage and wetted in that location. FIG. 4A, 4B and 4C demonstrate this concept, and the reading generated from this initial process may be converted into a contour map or numerical table indicating high and low voltage areas, with the high voltage areas indicating the possible locations of leaks in the membrane. If the area is extensive enough, these readings may not definitely define the leak location, as other non-related elements, such as stray electrical influences in or on the roofing surface or in or on the overburden may also provide voltage signatures similar to a leak. These signatures may be large enough to blind the actual leak signal, making determination of the leak difficult, if not impossible. To mitigate this interference, one or more of the attractor cables is activated. Because the attractor cables are also referenced to the power supply, they affect the flow of current on the surface of the roofing as it relates to the electricity emanating from the leakage area. As such, they change the shape of the voltage signature from the leak, which is the other side of the reference because the leak allows water to reach the conductive mesh. The voltage signatures that are not part of the referenced circuit, i.e. the signatures created by stray electrical influences, will not change substantially with the activation of the attractor cables. Activation of the attractor cable or cables also increase the measured voltage at or near the source of the leakage, which is another clue that the leak is in that particular area. The attractor cables may be activated one at a time or all at once. Experimentation has shown that activating one attractor cable by itself, or two attractor cables disposed at an angle to one another produces good results in identifying the area and location of leakage.
In its most basic form, the method for detecting and locating leaks in a roofing membrane includes the following steps: Installing a system, which includes the steps of installing a conductive mesh underneath of a roofing membrane; connecting the conductive mesh to a power supply such that the power supply powers the conductive mesh; installing sensors on top of the roofing membrane; installing at least one attractor cable on top of the roofing membrane; connecting the attractor cables to the power supply such that they are referenced to the power supply; electronically connecting the conductive mesh, the power supply, the sensors, and each attractor cable to a computer that executes software for communicating with and/or controlling these elements; energizing the conductive mesh; polling the sensors for voltage readings for a first time; developing a voltage contour map or table from the first polling readings; activating one or more of the attractor cables; polling the sensors for voltage readings for a second time; developing a voltage contour map or table from the second polling readings; comparing the contour maps or tables from the first and second polling readings; and identifying a location of a leak from the compared first and second contour maps or tables.
The step of installing sensors may be accomplished in several different ways. In one embodiment, this step involves installing wired sensors and connecting the wired sensors to the power supply such that they are referenced to the power supply. In another embodiment, the step involves installing a wireless sensor that is referenced to ground or the common of the building and includes a single wire, and connecting that single wire to anywhere on the building. If this step of installing a wireless sensor is performed, then the additional step of referencing the power supply and the attractor cables to a common ground is also required.
In some embodiments, the steps of activating one or more of the attractor cables; polling the sensors for voltage readings for an nth time; and developing a voltage contour map or numerical table from the nth polling readings may be repeated.
In some embodiments, the method also includes the step of placing a moisture permeable felt or other fabric on top of the sensors and attractor cables.
In some embodiments, the method also includes the step of manually activating the attractor cables in order to get increased readings at a specific sensor. This step checks the validity of data received from the computer running the method. If a problem is suspected, a specific attractor with a known disposition relative to a sensor in question may be activated.
In its most basic form, the system for detecting and locating leaks in roof flashing of the present invention includes at least one segment of a conductive medium disposed behind the roof flashing to be tested; at least one attractor cable; a power supply attached to the attractor cables and the conductive medium behind the flashing; and a computer in electronic communication with the power supply, the conductive medium, and the attractor cable or cables.
The conductive medium may be any metal mesh, conductive felt, scrim, or coating. The conductive medium may be the same material as the conductive mesh discussed above with reference to the system for detecting and locating leaks in a roofing membrane of the present invention. Although they may be the same material, “conductive mesh” is used in reference to the system for a roofing membrane and “conductive medium” is used in reference to the system for roof flashing, so as to avoid confusion as to which system is being discussed. Importantly, if this system for detecting leaks in roof flashing is used in conjunction with the system for detecting leaks in roof membranes, the conductive medium of this roof flashing system cannot touch and must be independent from and not connected to the conductive mesh of the roof membrane system. The conductive medium essentially acts as a large sensor, as discussed below, which is why additional sensors are not required for this system for detecting leaks in roof flashing, although they may be added optionally, also as discussed below. It is segmented so that when it indicates a possible leak, the leak may be localized to the position of that specific segment of conductive medium. Generally, the size of the segments is dependent on the length of the flashing to be tested and the desire to have a certain degree of resolution or localization of leakage. Several segments may be used for long portions of flashing. The more segments of conductive medium that are used, the more localized a potential leak may be. More segments require more electrical connections and a generally more cumbersome system, however. Segments should not touch, as two touching segments will act as one large segment, thus minimizing the localization advantage of having multiple segments. Designers may therefore use their best judgement in determining the size and number of conductive medium segments. The conductive medium cannot touch any conductive elements from the building or other elements not referenced to the return side of the power supply. This system for detecting leaks in roof flashing is distinct from the system for detecting leaks in roof membranes because roof flashing and roof membranes are distinct. The segmentation of the conductive medium in the system for roof flashing is also distinctive over the continuous conductive mesh used in the system for roof membranes.
The attractor cables are as described above with reference to the system for detecting and locating leaks in a roofing membrane of the present invention. The computer is also as described above with reference to the system for detecting and locating leaks in a roofing membrane of the present invention.
It is preferred that the conductive medium be referenced to the power supply and the attractor cable be powered by the power supply. The system works with the reverse polarity as well, however, with the conductive medium powered by the power supply and the attractor cable referenced to the power supply, similar to the system for roofing membranes of the present invention. Discussions herein refer to the former preferred embodiment, but it is understood that the reverse is also possible.
In some embodiments, this system also includes one or more wireless readers disposed on the conductive medium behind the flashing. The wireless reader is referenced to ground or common, so long as the power supply is referencing the same common. This is so that voltage from the live attractor cables can be detected behind the flashing by the conductive medium and the wireless reader if there is a leak. This is all that is necessary, as exact voltage measurements for triangulation are not necessary in this application, as opposed to similar applications on a roofing membrane, for example. Instead, it is only necessary that a change in voltage be detectable at the segment of the conductive medium where the leak exists.
In practice, the attractor cables are energized. A leak in the flashing may be in the body of the material of the flashing; in the welds that seal the flashing to the body of the roofing membrane; or in the sheets of flashing stuck together. If there is a leak in the flashing, the circuit between the segment of conductive medium and the power supply will complete. The completion of the circuit will be indicated in a potential spike in the contour map or numeric table readings corresponding to that segment.
In its most basic form the method for detecting and locating leaks in a roof flashing includes the following steps: Installing a system, which includes the steps of installing at least one segment of conductive medium behind the roof flashing; connecting the conductive medium to a power supply such that the segments are referenced to the power supply; installing at least one attractor cable proximate to the roof flashing; connecting the attractor cables to the power supply such that they are powered by the power supply; electronically connecting the conductive medium, the power supply, and the attractor cables to a computer that executes software for controlling these elements; energizing the attractor cables; observing a completed circuit between one of the conductive medium segments; and determining a leak location based on the location of the conductive medium segment that completed the circuit.
In some embodiments, the step of installing a system also includes the step of installing at least one wireless reader on each segment of conductive medium installed behind the flashing.
In its most basic form, the system for detecting and locating leaks in roofing membranes and roof flashing includes both the system for detecting and locating leaks in roofing membranes and the system for detecting and locating leaks in roof flashing, as described above. This combined system may be referred to herein as the “compound system.” As mentioned, the conductive mesh of the roofing membrane system cannot be in contact with a segment of conductive medium of the roof flashing system. One computer may be used to control the compound system, so long as it can control all of the aspects described above with reference to either system. One power supply may be used for the compound system. It is particularly important for the polarity of that power supply to be reversible when referenced from the attractor cables or the conductive mesh. Although it is theoretically possible that only one attractor cable may be used for the entire compound system, it is preferred that several are placed near the flashing and around the roofing area to be tested.
The method for detecting and locating leaks in roofing membranes and roof flashing includes the steps listed above for both the roofing membrane method and the roof flashing method.
These aspects of the present invention are not meant to be exclusive and other features, aspects, and advantages of the present invention will be readily apparent to those of ordinary skill in the art when read in conjunction with the following description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a top down diagram of a prior art leak detection system in use on a roofing membrane.
FIG. 1B is a graph of potential across one horizontal section of the membrane being tested for leaks in FIG. 1A .
FIG. 1C is a side diagram across one horizontal section of the membrane being tested for leaks in FIG. 1A .
FIG. 2A is a top down diagram of a leak detection system of the present invention in use on a roofing membrane.
FIG. 2B is a graph of potential across one horizontal section of the membrane being tested for leaks in FIG. 2A .
FIG. 2C is a side diagram across one horizontal section of the membrane being tested for leaks in FIG. 2A .
FIG. 3A is a top down diagram of a leak detection system for roofing membranes and roof flashing in use with a roofing membrane, including its flashing.
FIG. 3B is a graph of potential across one horizontal section of the membrane being tested for leaks in FIG. 3A , including its flashing.
FIG. 3C is a side diagram across one horizontal section of the membrane being tested for leaks, including its flashing, in FIG. 3A .
FIG. 4A is a top down diagram of a leak detection system for roofing membranes showing the effect that alternately isolated wet areas with leakage, wet areas without leakage, and dry areas have on the reading of the sensors.
FIG. 4B is a graph of potential across one horizontal section showing the effect of the areas as shown in FIG. 4A .
FIG. 4C is a side diagram across one horizontal section showing the effect of the areas as shown in FIG. 4A .
DETAILED DESCRIPTION
Referring first to FIG. 2A , a top down diagram of a leak detection system of the present invention is provided. Roofing membrane 14 is disposed on top of conductive mesh 4 . An array of sensors 1 are surrounded by four non-attached attractor cables 2 .
Power supply 5 powers conductive mesh 4 and is referenced by both sensors 1 and attractor cables 2 . Membrane 14 has a leak 6 and a stray electrical influence 7 .
When conductive mesh 4 is powered, sensors 1 provide voltage information that may be converted into a contour map that may look similar to that shown in FIG. 1B . In other words, both actual leak 6 and stray electrical influence 7 are indicating the location of possible leaks. When one or more attractor cables 2 are activated, however, the shape of the contour map changes to FIG. 2B . Leak 6 will cause water to contact conductive mesh 4 . Stray electrical influence 7 will not. As attractor cables 2 , sensors 1 , and conductive mesh 4 are all attached to power supply 5 , and stray electrical influence 7 is independent from it, activating attractor cables 2 will affect the voltages read by sensors 1 near leak 6 , but not those read by sensors 1 near stray electrical influence 7 . When used in conjunction with a map of the membrane 14 , as shown in FIG. 2C , a comparison of the contour maps shown in FIG. 1B , created by energizing conductive mesh 4 alone, and FIG. 2B , created by energizing conductive mesh 4 and activating attractor cables 2 , the location of 6 is provided and it is clear that leak 6 is the actual leak.
Now referring to FIG. 3A , a top down diagram of a leak detection system for roofing membranes and roof flashing in use with a roofing membrane 14 , including its flashing 3 , is provided. Roofing membrane 14 is surrounded by flashing 3 . The lettered segments of dotted lines around flashing 3 and membrane 14 indicate segments of conductive medium 10 behind flashing 3 . Flashing 3 has a leak 12 . Conductive medium 10 segment A is behind flashing 3 where leak 12 occurs.
Power supply 5 powers attractor cables 2 . Conductive medium 10 segments are referenced to power supply 5 . When attractor cables 2 are activated, the circuit will only be completed at conductive medium 10 segment A where leak 12 occurs. This is indicated by spike 13 in potential on the contour map shown in FIG. 3B . Spike 13 corresponds with the location of conductive medium 10 segment A, as shown in FIG. 3C , indicating the location of leak 12 .
The system described with reference to FIGS. 2A-2C is also shown in FIGS. 3A-3C . Power supply 5 is attached to each of the elements discussed with reference to those figures. By reversing the polarity of power supply 5 , the elements may be alternately powered or referenced by power supply 5 . One of ordinary skill in the art will recognize that the changes in the contour map that are necessary to identify the location of an actual leak may be effected with the power flowing in either direction.
Now referring to FIGS. 4A-4C , the effects on the systems for leak detection and location of the present invention of alternately isolated wet areas with leakage 15 , wet areas without leakage 17 , and dry areas 16 are illustrated. As shown, only wet areas with leakage 15 will cause the system to measure a potential difference. Therefore only the leak 6 will be identified by the system. Non-problematic, non-leaking wet or dry areas 17 , 16 will correctly escape the systems' attention. Attractor cables 2 aid in defining the location of a leak 6 on a wider area basis, and may help eliminate stray voltage signatures from other elements in the overburden. Where a local area is wet and there is a leak 15 , however, this will still be indicated in the leak detection system as a voltage spike emanating from the sensors 1 close to the area of leakage 15 and wetted in that location. The reading generated from this initial process may be converted into a contour map or numerical table indicating high and low voltage areas, such as FIG. 4B , with the high voltage areas indicating the possible locations of leaks in the membrane.
Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions would be readily apparent to those of ordinary skill in the art. Therefore, the spirit and scope of the description should not be limited to the description of the preferred versions contained herein.
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The present invention is systems and methods for detecting and locating leaks in roofing membranes and roof flashing. The systems include a conductive mesh underneath the roofing membrane and/or a conductive medium behind the roof flashing; attractor cables; and a reversible power supply attached to the conductive mesh/medium and attractor cables. The roofing membrane system also includes sensors, which may be wireless. The systems are controlled by a computer.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Patent Application Ser. No. 60/663,128, filed Mar. 18, 2005; and is a continuation application of U.S. patent application Ser. No. 10/842,357, filed May 10, 2004; the disclosures of which are incorporated herein by reference in their entireties.
GOVERNMENT INTEREST
[0002] This invention was made with U.S. Government support under grant number 5-5-58595 awarded by the National Aeronautics and Space Administration (NASA). The U.S. Government has certain rights in the invention.
TECHNICAL FIELD
[0003] The subject matter described herein relates to methods and systems for attaching nanostructures to objects and apparatuses formed therefrom. More particularly, the subject matter described herein relates to methods and systems for attaching one or more magnetic nanowires to an object and apparatuses formed therefrom, and to an electrophoresis method for fabrication of magnetic force microscopy probes using magnetic nanowires.
BACKGROUND ART
[0004] Magnetic force microscopy (MFM) is a non-destructive, experimental technique for investigation of surface magnetic structure of systems such as magnetic storage media. The resolution and sensitivity of MFM depends largely on the geometry and magnetic properties of the MFM's probe. MFM probes are typically fabricated by coating a tip of an atomic force microscope (AFM) cantilever with a layer of hard ferromagnetic materials such as cobalt-based alloy. This process increases the tip radius of the probe. By increasing the probe's tip radius, the spatial resolution of the MFM may be increased to an order of 100 nm. Therefore, it is desirable to reduce the tip radius of MFM probes.
[0005] Techniques have been investigated and developed for producing MFM probes with reduced radii. These techniques include the use of either electron beam deposition or focused ion beam milling. In one technique, carbon nanotubes (CNTs) are grown and attached to the apex of a silicon cantilever of a probe. CNTs have nanometer-size diameters and large aspect ratios. The use of CNTs increases the spatial resolution and probing depth of AFMs.
[0006] Several different techniques have been developed to produce MFM probes including CNTs. In one technique, a single, multi-wall carbon nanotube (MWNT) capped with a magnetic catalyst particle is mounted onto the apex of a commercial silicon cantilever inside the chamber of a scanning electron microscope (SEM). In another technique, a carbon nanofiber was grown on a tipless Si cantilever using direct chemical vapor deposition (CVD). In the tip-growth CVD process, the encapsulated magnetic particle is positioned at the top of the nanofiber and provides the magnetic force. In yet another technique, MFM probes are produced by sputtering a layer of magnetic film onto the outer surface of a CNT either mounted or catalytically grown on a silicon cantilever. Although the imaging results obtained by using CNT magnetic probes are good, it is desirable to provide probes having improved resolution and probing depth.
[0007] In view of the shortcomings of existing magnetic microscopy devices, there exists a need for providing methods and systems for improving the performance and manufacture of these devices as well as the apparatuses produced therefrom.
SUMMARY
[0008] In accordance with this disclosure, novel systems and methods are provided for attaching a magnetic nanowire to an object and apparatuses produced therefrom and for electrophoretic fabrication of magnetic force microscopy probes using magnetic nanowires.
[0009] It is an object of the present disclosure therefore to provide novel systems and methods for attaching a magnetic nanowire to an object and apparatuses produced therefrom and to provide a novel electrophoresis method for fabrication of magnetic force microscopy probes using magnetic nanowires in order to improve the manufacture and resolution of devices such as magnetic microscopy devices. This and other objects as may become apparent from the present disclosure are achieved, at least in whole or in part, by the subject matter described herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] Exemplary embodiments of the subject matter will now be explained with reference to the accompanying drawings, of which:
[0011] FIG. 1 is a schematic diagram of an exemplary system for attaching one or more magnetic nanowires to a sharp tip of an object according to an embodiment of the subject matter described herein;
[0012] FIG. 2 is a flow chart of an exemplary process for attaching one or more magnetic nanowires to a sharp tip of an object according to an embodiment of the subject matter described herein;
[0013] FIG. 3 is a TEM image of nickel magnetic nanowires synthesized by an electrodeposition method according to an embodiment of the subject matter described herein;
[0014] FIG. 4 is a schematic diagram of an atomic force microscope cantilever having a single magnetic nanowire attached to a tip of the cantilever according to an embodiment of the subject matter described herein;
[0015] FIG. 5 is a schematic diagram of an atomic force microscope cantilever having several magnetic nanowires attached to a tip of the cantilever according to an embodiment of the subject matter described herein;
[0016] FIG. 6 is an SEM image of exemplary magnetic probes having nickel magnetic nanowires attached according to an embodiment of the subject matter described herein;
[0017] FIG. 7 is another SEM image of exemplary magnetic probes having nickel magnetic nanowires attached according to an embodiment of the subject matter described herein;
[0018] FIGS. 8, 9 , and 10 are SEM images of exemplary magnetic force microscopy probes including nickel magnetic nanowires attached according to an embodiment of the subject matter described herein;
[0019] FIG. 11 is a topographic image of a magnetic recording tape obtained using an atomic force microscope having magnetic nanoparticles according to an embodiment of the subject matter described herein;
[0020] FIG. 12 is a magnetic image of a magnetic recording tape obtained using an atomic force microscope having magnetic nanoparticles according to an embodiment of the subject matter described herein;
[0021] FIG. 13A is a graph showing a height profile of a calibration sample measured using a conventional Si atomic force microscope probe;
[0022] FIG. 13B is a graph showing a height profile of a calibration sample measured using an atomic force microscope probe including a nickel magnetic nanowire attached according to the subject matter described herein; and
[0023] FIG. 13C is a graph showing a height profile of a calibration sample measured using an atomic force microscope probe including a carbon nanotube attached thereto.
DETAILED DESCRIPTION
[0024] Systems and methods according to the subject matter described herein can be used for attaching one or more magnetic nanowires onto a sharp tip of an object. For example, systems and methods according to the subject matter described herein can be used for attaching one or more magnetic nanowires to a sharp tip of an atomic force microscope.
[0025] FIG. 1 illustrates a schematic diagram of an exemplary system generally designated 100 for attaching one or more magnetic nanowires MN to a sharp tip TP of an object O according to an embodiment of the subject matter described herein. In this example, object O can be a cantilever of an atomic force microscope. Alternatively, object O can be part of a profilometer, a probe, electron a field emission cathode, a gas discharge tube, a lighting device, a microwave power amplifier, an ion gun, an electron beam lithography device, a high energy accelerator, a free electron laser, and a flat panel display. System 100 can include an electrode E, a power source PS, and a liquid medium generally designated LM. Electrode E, tip TP, and magnetic nanowire MN can be positioned in liquid medium LM. Power source PS can apply a voltage difference between tip TP and electrode E for generating an electrical field (generally designated EF) in liquid medium LM. Electrical field EF can cause magnetic nanowire MN to migrate towards tip TP (in the direction indicated by direction arrow A) and attach to tip TP. In particular, an end of magnetic nanowire MN can attach to tip TP.
[0026] FIG. 2 is a flow chart illustrating an exemplary process for attaching one or more magnetic nanowires to a sharp tip of an object according to an embodiment of the subject matter described herein. In this example, the magnetic nanowires are attached via a positive dielectrophoresis process. Referring to FIG. 2 , in block 200 , magnetic nanowires can be synthesized or otherwise produced. The magnetic nanowires can be fabricated by electrodeposition using an anodic alumina template with 15-50 nm diameter holes. The electrodeposition can be conducted at room temperature or any other suitable temperature. A water solution containing nickel sulfate and boric acid can be used as an electrolyte. After electrodeposition, the nanowires can be harvested by dissolving the alumina template in phosphoric acid at room temperature or another suitable temperature. The nanowires can then be dispersed in de-ionized water without surfactants, centrifuged, and homogenized in an ultrasonic bath.
[0027] A magnetic nanowire can be a nanowire that comprises at least one of the following magnetic materials: nickel (Ni), cobalt (Co), and iron (Fe).
[0028] FIG. 3 illustrates a TEM image of nickel magnetic nanowires synthesized by an electrodeposition method according to an embodiment of the subject matter described herein. The lengths of the nanowires vary from about 300 nm to 800 nm in length. The diameters of the nanowires are between about 20 and 40 nm.
[0029] The magnetic nanowires can be optionally purified by several techniques including filtration, centrifuge, and chromatography to separate the nanowires from the impurities and to sort the nanowires based on diameter and length. The magnetic nanowires can then be subjected to further processing to shorten the length, such as by chemical etching or by mechanical processes such as ball milling.
[0030] According to another embodiment, the purified magnetic nanowires can be shortened by mechanical milling. According to this technique, a sample of the purified magnetic nanowire material is placed inside a suitable container, along with appropriate milling media. The container is then shut and placed within a suitable holder of a ball-milling machine. The time that the sample is milled can vary. An appropriate amount of milling time can be readily determined by inspection of the milled nanowires.
[0031] Referring again to FIG. 2 , in block 202 , the magnetic nanowires can be provided in a liquid medium such as liquid medium LM shown in FIG. 1 . The liquid medium can be selected which will permit the formation of a stable suspension of the raw nanowires therein. According to one embodiment, the liquid medium comprises at least one of the following: de-ionized water, methanol, ethanol, alcohol, and dimethylformamide (DMF). Upon adding the nanowires to the liquid medium, the mixture can be subjected to ultrasonic energy or stirring using, for example, a magnetic stirrer bar, in order to facilitate the formation of a stable suspension. The amount of time that the ultrasonic energy is applied can be a suitable time, such as about two hours.
[0032] In block 204 , a sharp tip of an object can be positioned in the liquid medium. For example, sharp tip TP of object O can be gradually moved from a position outside of liquid medium LM to a position within liquid medium LM as shown in FIG. 1 . In one embodiment, electrode E can be a metallic ring positioned in liquid medium LM. Further, electrode E and object O can be mounted on separate translation stages and placed under an optical microscope for observation. Electrode E can be translated to contact liquid medium LM and moved to a position as shown in FIG. 1 . Tip TP can be positioned in liquid medium LM for a predetermined period of time. Further, tip TP can be moved towards liquid medium LM until an electrical contact is established between electrode E and tip TP.
[0033] In block 206 , an electrical field can be applied to the liquid medium for attaching the magnetic nanoparticles to the sharp tip. Power source PS can be controlled to apply a voltage across object O and electrode E for generating an electrical field between object O and electrode E for a predetermined period of time. When the voltage is applied to object O and electrode E, object O can be function as an electrode. Further, the applied voltage can be variably controlled to apply an alternating current (AC) or direct current (DC) to object O and electrode E. In one example, the applied voltage can be about 1-10 V at 2 MHz. The electrical field can cause magnetic nanoparticles to migrate towards sharp tip TP and attach to sharp tip TP. The electrical field applied between object O and electrode E can be about 0.1-1000 V/cm, and a DC of 0.1-200 mA/cm 2 can be applied for 1 second-1 hour.
[0034] Under guidance of an optical microscope, electrode E can be withdrawn from liquid medium LM during application of the electrical field. One end of one or more magnetic nanowires can attach to sharp tip TP. The attached magnetic nanowires can form a magnetic tip with tip TP. The length of the magnetic tip can be controlled by the distance by which object O and electrode E are moved away from one another under the electrical field. Movement of object O and electrode E away from one another under the electrical field can cause the nanowires to straighten and align in the direction of the movement.
[0035] In one embodiment, after assembly of one or more magnetic nanowires with an object, a protective material can be applied to the magnetic nanowires and/or the object. One example of the protective material is a layer of polymer coating which can protect the nanowire from damage and increase the mechanical stability of the assembled structure.
[0036] According to one embodiment, a “charger” can be added to the liquid medium in order to facilitate electrophoretic deposition. Exemplary chargers include MgCl 2 , Y(NO 3 ) 3 , AlCl 3 , and sodium hydroxide. Any suitable amount can be utilized. Amounts ranging from less than about 1% up to about 50%, by weight, as measured relative to the amount of nanowire-containing material, can be used. According to another embodiment, the liquid medium can contain less than 1% of the charger.
[0037] The direction in which the magnetic nanowires migrate can be controlled through the selection of the charger material. For example, the user of a “negative” charger, such as sodium hydroxide (NaOH) imparts a negative charge to the nanowires, thereby creating a tendency for the nanowires to migrate towards the positive electrode (cathode). Conversely, when a “positive” charger material is used, such as MgCl 2 , a positive charge is imparted to the nanowires, thereby creating a tendency for the nanowires to migrate toward the negative electrode (anode).
[0038] The adhesion of magnetic nanowires can be improved by incorporation of adhesion promoting materials such as binders. These materials can be introduced by, for example, one of the following processes: co-deposition of the nanowires and particles of adhesion promoting materials, sequential deposition, pre-deposition of a layer of adhesion promoting materials, and the like. In one example, a magnetic nanowire can be annealed for attaching to a sharp tip of an object. The annealing can occur at a suitable temperature, such as 100° C. to 600° C. Further, a magnetic nanowire can be annealed for a suitable time period, such as approximately 1 to 60 minutes. Annealing can occur at a pressure of about 10 −6 Torr or another suitable vacuum pressure.
[0039] In one embodiment, binders such as polymer binders can be added to a suspension of magnetic nanowire material which is then either stirred or sonicated to obtain a uniform suspension. Suitable polymer binders include poly(vinyl butyral-co vinyl alcohol-co-vinyl acetate) and poly(vinylidene fluoride). Suitable chargers are chosen such that under the applied electrical field, either DC or AC, the binder and the nanostructures would migrate to the same electrodes to form a coating with an intimate mixing of the nanostructures and the binder.
[0040] The binders or adhesion promoting materials can be added in any suitable amount. Amounts ranging from 0.1-20% by weight, measured relative to the amount of nanostructure-containing material can be provided.
[0041] FIG. 4 illustrates a schematic diagram of an atomic force microscope cantilever C having a single magnetic nanowire MN attached to a tip TP of cantilever C according to an embodiment of the subject matter described herein. Referring to FIG. 4 , an end of magnetic nanowire MN is attached to tip TP of cantilever C. Further, nanowire MN can be substantially straight and aligned with a cone axis of cantilever C. The direction of alignment of nanowire MN is the same as the direction of the electrical field applied during attachment. A tip 400 of the assembly of magnetic nanowire MN and cantilever C can have a single magnetic domain.
[0042] FIG. 5 illustrates a schematic diagram of an atomic force microscope cantilever C having several magnetic nanowires MN 1 , MN 2 , and MN 3 attached to a tip TP of cantilever C according to an embodiment of the subject matter described herein. Referring to FIG. 5 , ends of magnetic nanowires MN 1 and MN 2 can be attached to or near a tip of cantilever C by an attachment process described herein. Further, magnetic nanowire MN 3 can be attached to magnetic nanowires MN 1 and MN 2 by an attachment process described herein. Magnetic nanowires MN 1 , MN 2 , and MN 3 can be substantially aligned with a cone axis of cantilever C and with one another. A tip 500 of the assembly of magnetic nanowires MN 1 , MN 2 , and MN 3 and cantilever C can have a single magnetic domain.
[0043] FIGS. 6 and 7 are SEM images of exemplary magnetic probes having nickel magnetic nanowires attached according to an embodiment of the subject matter described herein. The probe tip is about 2 μm in length and about 30 nm in diameter at its tip. A bundle of magnetic nanowires are attached to the tip of the probe. A single magnetic nanowire protrudes from the bundle and, provides the small tip diameter. Probes formed using cobalt magnetic nanowires have a similar structure and morphology as probes formed using nickel magnetic nanowires.
[0044] FIGS. 8, 9 , and 10 are SEM images of exemplary magnetic force microscopy probes including nickel magnetic nanowires attached according to an embodiment of the subject matter described herein. The probes include nanowires of different length and morphology. These probes were annealed under 10 −6 Torr vacuum. During experimentation, it was found that the Ni and the Co nanowires recrystallized into large particles when annealed at temperatures above 800° C. Annealing at 750° C. for about one hour can improve adhesion between the individual nanowires forming the tip, although conglomeration of the metal coating on the Si cantilever was observed after annealing.
[0045] By varying the conditions such as concentration and dispersion of magnetic nanowires in a liquid medium, the electrical field strength, and the rate at which an object tip is withdrawn from a liquid medium surface, the spacing and the alignment of magnetic nanowires on the object tip can be altered.
[0046] FIGS. 11 and 12 are a topographic image and a magnetic image, respectively, of a magnetic recording tape obtained using an atomic force microscope having magnetic nanoparticles according to an embodiment of the subject matter described herein. The microscope was magnetized prior to imaging. The microscope probe with nickel nanowires used for imaging included a tip diameter of about 30 nm over a 4 μm×4 μm area. The images demonstrate that improved spatial resolution can be obtained by attachment of magnetic nanowires according to the systems and methods described herein.
[0047] FIGS. 13A-13C illustrate graphs showing height profiles of a calibration sample measured using different atomic force microscope probes. FIG. 13A shows the measured height profile provided by a conventional Si atomic force microscope probe. FIG. 13B shows the measured height profile provided by an atomic force microscope probe including a nickel magnetic nanowire attached according to the subject matter described herein. FIG. 13C shows the measured height profile provided by an atomic force microscope probe including a carbon nanotube attached thereto. The sidewall angles measured in FIGS. 13A-13C are 68°, 78°, and 84°, respectively. The actual sidewall angle is 90°.
[0048] The systems and methods according to the subject matter described herein can be used for incorporating magnetic nanowires into profilometers and probes for electron microscopes, electron field emission cathodes for devices such as x-ray generating devices, gas discharge tubes, lighting devices, microwave power amplifiers, ion guns, electron beam lithography devices, high energy accelerators, free electron lasers, and flat panel displays. For example, the methods described herein can be used to deposit a single or a bundle of nanowires selectively onto a sharp tip. The sharp tip can be, for example, the tip used for microscopes including scanning tunneling microscopes (STMs), magnetic force microscopes (MFMs), and chemical force microscopes (CFMs).
[0049] Further, the system and methods according to the subject matter described herein can be used for attaching any suitable conductive nanoparticle to a sharp tip. For example, the systems and methods can be used for attaching a nanotube, such as a carbon nanotube, including a magnetic material to a sharp tip. A nanotube structure having a composition of B x C y N, (B=boron, C=carbon, and N=nitrogen), or nanotube or concentric fullerene structures with a composition MS 2 (M=tungsten, molybdenum, or vanadium oxide) can be utilized.
[0050] It will be understood that various details of the subject matter described herein may be changed without departing from the scope of the subject matter described herein. Furthermore, the foregoing description is for the purpose of illustration only, and not for the purpose of limitation.
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Methods and systems are provided for attaching one or magnetic nanowires to an object and apparatuses formed therefrom. An electrophoresis method for attaching one or more nanowires to a sharp tip of an object can include including providing one or more magnetic nanowires in a liquid medium. The method can also include positioning a sharp tip of an object in the liquid medium. Further, the method can include applying an electrical field to the liquid medium for attaching the one or more magnetic nanowires to the sharp tip.
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CLAIM OF PRIORITY
This application claims the priority of U.S. Ser. No. 61/873,146 filed on Sep. 3, 2013, the contents of which are fully incorporated herein by reference.
FIELD OF THE INVENTION
The field of the invention relates to a sports training apparatus, namely devices designed to elicit a sport specific movement. In particular, the present invention is a guide assembly for teaching and/or correcting a baseball player's swing to the perfect swing.
BACKGROUND OF THE INVENTION
There is a great deal of debate on when the game of baseball started in the United States of America. However, the game most generally recognized as the first game played on American soil was in 1846. Thereafter, the game went through a number of rule revisions up until 1893. Since then, the rules of baseball have remained relatively unchanged. While the rules have remained the same, the approach to playing the game has seen a number of strategical advancements.
One such advancement is in the way batters swing their bat. For the longest time, batters have been taught to swing on an “A to C” plane. During this “A to C” swing, the player's hands move directly to the ball, and the barrel of the bat stays above the hands through the point of contact. This means that the players are taking the bat from behind their shoulder on a downward line and making contact with the lower portion of the ball and continuing their swing through the ball. Often times, especially in young ball players, this results in the batter's weight shifting forward in their stance and greatly reducing their power and momentum. The premise behind this swing style is that by hitting the lower portion of the ball and creating backspin, the ball will travel further off the bat. However, recent studies of the swings of some of the top baseball players in the world show a markedly different story.
Empirical evidence and an examination by the Entertainment and Sports Programming Network (ESPN) demonstrate that the bat should ideally follow a looping motion and be swung with a slight upswing through the ball in order to help maximize the flight path of the ball. In order to complete this swing, the rear shoulder must drop and the weight must be kept primarily over the back foot of the batter's stance. This means that the hands start out on a more curved path before making a hard turn to the right or left (depending on the handedness of the batter). This hard turn of the hands whips the head of the barrel out into the path of the ball with a slight upswing, propelling the ball substantially further than when one swings down the ball as described above. The inherent problem with the former swing style is not the ability to make contact with the ball, but rather the path of the ball. The “A to C” swing style creates a large number of groundballs. As players age, groundballs result in outs with an increased frequency. There is data to suggest that as many as 75% of groundballs result in outs in Major League Baseball (MLB). The looping swing style helps to propel the ball further and limit the amount of groundballs resulting in outs.
Thus, there is a need for an apparatus that assists to either teach or correct a batter's swing to enable them to maximize the flight path of the ball off the bat. This is done by providing a restricted swing area that mimics the preferred upswing motion. Additionally, there is a need for an apparatus that can be used and enjoyed by players that bat both left and right handed. There is another need for an apparatus that can progressively restrict a batter's swing to a predetermined swing path. There is also a need for an apparatus that can measure other factors related to the ball flight, such as bat speed, to help players achieve the maximum flight path. The current apparatus also requires the batter to prevent their weight from shifting forward during the swing in order to correctly and efficiently swing their bat through the apparatus. The current invention meets and exceeds all these limitations.
Review of Related Technology:
U.S. Pat. No. 5,087,039 pertains to a baseball bat swing training apparatus that includes a base which sits on the ground with a vertically extending post extending from the base. A baseball bat swing guide is attached to the post which has a pair of parallel swing guides connected at one end and open at the other end. The swing guide arms are positioned at a predetermined slope to the post of between 50 and 80 degrees. Each arm has an approximately 90 degree bend therein to form a bent U-shape. A ball holding cup can be attached to the lower arm while the ball holder can be attached to the upper arm and the vertically extending post is a telescoping post for adjusting the height thereof and may be a dual post. A second embodiment has a pair of posts and a pair of base members for supporting a pair of swing guide arms.
U.S. Pat. No. 4,577,863 pertains to a device that measures the height and inclination of a batter's swing plane by a batting practice device shaped like a home plate and including a laser source and photosensors for detecting laser light reflected by the bat when swung over the plate.
U.S. Pat. No. 3,904,199 pertains to a sports stroke training device having a post for mounting vertically on a vertical surface. The post is provided with a longitudinal groove for adjustably retaining a pivot shaft. An elongated bar is mounted intermediate its ends on the pivot shaft for pivotal movement thereon. The bar is provided at each of its ends with a flexible guide member which extends perpendicular from the bar in a direction from the post. A correct racket stroke is made when both guide members are hit during the stroke along the longitudinal centerline of the bar.
Various devices are known in the art. However, their structure and means of operation are substantially different from the present disclosure. In contrast to these devices, the current invention allows for an upward swinging/hitting angle, can be oriented for left or right handed batters, measures bat speed, and has an adjustable swing zone. Thus, the other inventions fail to solve all the problems taught by the present disclosure. At least one embodiment of this invention is presented in the drawings below and will be described in more detail herein.
SUMMARY OF THE INVENTION
A swing guide training apparatus is described and taught having a base member with a first vertical support of a specific diameter extending therefrom, wherein the first vertical support has a securing mechanism; a swing guide arm base attached to an upper end of a second vertical support, the second vertical support having a complimentary shape and having a smaller diameter than the first vertical support and is slidably coupled with the first vertical support to interact with the securing mechanism for maintaining the position of the second vertical support; a pitch assembly rotatably coupled to the swing guide arm base; a first swing guide arm coupled to the pitch assembly; and a second swing guide arm coupled to the first swing guide arm by an adjustable U-shaped member, wherein the first and the second swing guide arm are parallel to one another forming a swing guide assembly.
The swing guide training apparatus may have at least one ball holding mount extending from the swing guide arm base. The ball holding mount accepts a ball holding apparatus. This enables a ball to be positioned through the swing path for the batter to practice. In some instances, the swing training guide apparatus may have a measurement device, such as radar, to measure the speed of the bat as it is swung through the swing guide assembly. The measuring device is preferably attached to the adjustable U-shaped member. In order to prevent damage to the apparatus, it may be desirable to have protective coverings on each of the swing arms. These are preferably a strong, flexible tubing such a polyethylene. The base member of the apparatus has an angled support and a plurality of support legs extending therefrom. These legs may be collapsible and may have non-slip coverings to keep the apparatus stable and upright.
As the batter becomes more proficient in using the apparatus, the adjustable U-shaped member can be compressed. Alternatively, it can also be expanded as needed. This, in turn, changes the diameter, or vertical distance, between the first and second swing guide arms. The securing mechanism is preferably a thumb screw clamp. This clamp allows for quick and easy changing of height of the apparatus. Finally, the swing guide assembly rotates about the vertical axis. This enables batters who are left and right handed to use the apparatus.
In general, the present invention succeeds in conferring the following, and others not mentioned, benefits and objectives.
It is an object of the present invention to provide a baseball swing training device.
It is an object of the present invention to provide a baseball swing corrective device.
It is an object of the present invention to provide a baseball swing training device that forces a player to swing slightly upwards.
It is an object of the present invention to provide a baseball swing training device that is rotatable and can be used by left handed and right handed batters.
It is an object of the present invention to provide a baseball swing training device that can adjust in height to accommodate batters of varying stature.
It is an object of the present invention to provide a baseball swing training device that can adjust the pitch of the device thereby allowing batters to swing on differing trajectory planes.
It is an object of the present invention to provide a baseball swing training device that can widen or narrow the swing channel to accommodate batters of differing abilities.
It is an object of the present invention to provide a baseball swing training device that measures that speed of the batter's bat as it passes through the device.
It is an object of the present invention to provide a baseball swing training device that allows a batter to hit a ball.
It is an object of the present invention to provide a baseball swing training device that is lightweight and portable.
It is an object of the present invention to provide a baseball swing training device that is resistant to damage from bats.
It is an object of the present invention to provide a baseball swing training device that enables the batter to maximize the flight path of the baseball.
It is another object of the present invention to provide a baseball swing training device that forces a batter's weight remain positioned over their back foot.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a preferred embodiment of the present invention.
FIG. 2 is a side view along plane A-A′ of a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The preferred embodiments of the present invention will now be described with reference to the drawings. Identical elements in the various figures are identified, as far as possible, with the same reference numerals. Reference will now be made in detail to embodiments of the present invention. Such embodiments are provided by way of explanation of the present invention, which is not intended to be limited thereto. In fact, those of ordinary skill in the art may appreciate upon reading the present specification and viewing the present drawings that various modifications and variations can be made thereto without deviating from the innovative concepts of the invention.
Referring to FIG. 1 , the preferred embodiment of the present invention is shown. The swing guide training apparatus 1 has a base member 14 . The base member 14 has an angled support 15 and a plurality of support legs 17 . The angled support 15 may be one continuous support piece, or it may be multiple pieces affixing to the sides of the first vertical support 19 . Each of the plurality of support legs 17 may move independent of one another and may be collapsible. The collapsible legs will help aid in the storage of the apparatus 1 . The support legs 17 may further have non-slip coverings 21 . These non-slip coverings 21 may comprise a number of slip resistant materials including but not limited to rubber, neoprene, and silicone. Some embodiments may have an attachment or feature that permits the apparatus 1 to be staked into the ground for increased stability.
Extending from the base member 14 is a first vertical support 19 . The first vertical support 19 is connected to the base member by a weld. Alternatively, the first vertical support 19 may be an extension of the base member 14 itself. Ideally, the first vertical support 19 is polygonal in shape having thickness with a hollow interior. The diameter of this support 19 can vary from about 2.5 cm (1 inch) to about 25 cm (10 inches). Preferably, the diameter is about 7.5 cm (3 inches). Alternatively the support 19 may be circular. The first vertical support 19 further has a securing mechanism 18 extending therethrough. The securing mechanism 18 is preferably a thumb screw clamp. This permits the securing mechanism 18 to be turned through a threaded opening in the first vertical support 19 thereby holding the second vertical support 16 in place.
The second vertical support 16 is smaller in diameter than the first vertical support 19 , but has a similar, complimentary shape. The diameter of the second vertical support 16 is such that it fits and slides within the first vertical support 19 . In some embodiments, it may be preferable that it is the second vertical support 16 has the larger diameter and the first vertical support 19 has the smaller diameter. This configuration does not change the inherent functionality of the apparatus 1 .
Attached to the top end of the second vertical support 16 is a swing guide arm base 30 . The swing guide arm base 30 is a rectangular piece of hardened plastic, rubber, or metal. On at least one end of the swing guide arm base 30 is a ball holding mount 26 . Preferably, the ball holding mount 26 is a threaded bolt connected to the swing guide arm base 30 . The ball holding mount 26 may also be smooth or coated with a tacky surface. Ideally, there is a ball holding mount 26 on each end of the swing guide arm base 30 . This would allow a ball holding apparatus 28 to be placed on either end. Thus, the ball holding apparatus 28 could be moved to either side to accommodate a left or right handed batter. The ball holding mount 26 can be a number of shapes and sizes that will allow the swing guide arm assembly 32 to rotate freely about the vertical axis.
Extending from the swing guide arm base 30 is a pitch assembly 20 which is attached to the first swing guide arm 10 . The pitch assembly 20 has a bracket with a plurality of holes (see FIG. 2 ) that enables the swing guide arm assembly 32 to move up and down. The swing guide arm assembly 32 can deviate up to about ±10° from its zero point and is held in place by another thumb screw. The general upward angle, above 90° relative to flat ground, creates the ideal swing pattern. It also forces a batter to keep their weight shifted to the rear of their stance. This promotes power and momentum throughout the duration of the swing, propelling the ball further. If the weight does come forward, the player will likely impact one of the protective coverings 12 or other part of the apparatus 1 . The batter can then reswing focusing on the placement of their body weight. The pitch assembly 20 not only changes the angle that one swings, but can further be used to make accommodations for players of differing statures in addition to changing the height of the apparatus 1 as a whole.
The first swing guide arm 10 and second swing guide arm 11 are coupled by an adjustable U-shaped member 22 . These elements form the foundation of the swing guide arm assembly 32 . The swing guide arms 10 , 11 can vary in length from about 0.5 m (20 inches) to about 1.0 m (39 inches) with an ideal length of about 0.8 m (31 inches). Each of the swing arms 10 , 11 are parallel to one another. They ideally have a hollow walled construction and are circular in shape. Alternate embodiments may call for varying shapes or a solid walled construction depending on the material composition of the swing guide arms 10 , 11 . Preferably, each of the swing guide arms 10 , 11 have a protective sheath 12 running the length of the swing guide arms 10 , 11 . This protective sheath 12 provides added protection against damage from bats to the swing guide arms 10 , 11 . Additionally, the inclusion of the protective sheath 12 may take some of the sting out a batter's hand if they hit either of the swing guide arms 10 , 11 . The protective sheath 12 should be flexible and may be any color. Acceptable materials may include polyurethanes, polyethylenes, nylons, polyvinylchlorides, polycarbonates, polypropylenes, and urethanes. This list is not exhaustive and may include other compounds exhibiting similar properties.
The swing guide arms 10 , 11 are coupled by a U-shaped member 22 . The U-shaped member 22 attaches to the under side of the first swing guide arm 10 and the upper side of the second swing guide arm 11 . This places each of the attachment sites outside of the path of the swing thereby not interfering with the swing or possibly causing damage to the bat. The U-shaped member 22 is preferably a flat, flexible metal band. This enables a user to bring the swing guide arms 10 , 11 closer together or pull them further apart. The swing guide arms 10 , 11 always remain on parallel planes. The decrease or increase in the diameter between the swing guide arms 10 , 11 changes the difficulty and precision needed to swing a bat through the apparatus 1 . The U-shaped member 22 may also have an attachment for a bat speed measuring device 24 . The bat speed measuring device may employ any number of tracking and speed calculation methods including but not limited to lasers, cameras, and radar.
FIG. 2 shows the present invention along plane A-A′ (see FIG. 1 ). Here, one can see clearly the components that form the heart of the invention. As the batter swings through the area defined by the first and second guide arm 10 , 11 the bat must swing at a slightly upwards angle or one will contact the guide arms. The batter may desire to have a ball holding apparatus 28 present through their swing path. This can be used with or without a baseball to ensure the swing trajectory is correct to make solid contact. There are ball holding mounts 26 on either side of the midline of the apparatus 1 . The swing guide arm assembly 32 is rotatable around the swing guide arm base 30 . Thus, a left handed or right handed batter can each use the apparatus 1 and the ball holding apparatus 28 as well. The pitch adjustment 20 has a bracket with a plurality of holes 29 that enables the pitch of the swing guide arm assembly 32 to change. The swing guide assembly 32 can change pitch to influence the batter's swing trajectory or to provide a fine tune adjustment for players of different statures. Each of these features are present upon a swing guide arm base 30 attached to the second vertical support 16 .
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A swing guide training apparatus may have a base with a vertical support where the vertical support can adjust the height of the apparatus. Opposite the base, there is a pair of swing guide arms forming a swing guide assembly. These swing guide arms are open on each end and are connected by a U-shaped member allowing a bat to be swung through the space provided by the swing guide assembly. The U-shaped member can be compressed or expanded to change the width of the swinging channel. Additionally, other features may be present such as a mount for holding a baseball and a device to measure the speed of the bat as it is swung through the swing channel. The swing guide assembly rotates to accommodate batters that are left and right handed.
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FIELD OF THE INVENTION
The present invention pertains to a partition system for subdividing a refrigerated chamber such as a truck trailer, railcar or cargo container.
BACKGROUND OF THE INVENTION
Refrigerated truck trailers and the like have long been used to transport perishable items. Insulated partitions or bulkheads have been used to subdivide the trailer interior to define chamber portions that can be maintained at different temperatures. For example, some trailers include multiple refrigerators located at the front, rear and/or midsection of the trailer's chamber. Partitions can be used to define two or three different refrigerated interior portions, each cooled to a unique temperature by one of the refrigerators. In this way, the same trailer can transport items that are desirably kept at different temperatures. Similarly, partitions can be used to enable refrigerated goods and non-refrigerated goods to be hauled in the same trailer. Partitions can also be used to improve the haul of a partially filled refrigerated truck trailer. For example, the goods can be loaded into one portion of the chamber, which is then enclosed by one or more partitions so that only a part of the trailer chamber needs to be refrigerated. Partitions can also be used to simply separate the goods to be delivered at different locations.
Many partitions in use today are manually fit into the truck trailer by the operator. They generally include a peripheral seal and extend laterally across the trailer chamber to subdivide the refrigerated chamber. They may at times be foldable about a vertical hinge to ease handling, installation and removal. In any event, the partitions tend to be heavy, bulky and difficult to place into their proper position. To resolve these difficulties, partitions have been shaped to correspond to only one-half of the trailer width in order to weigh less, and be more easily moved and put in place. In half-width partitions, two are placed in side-by-side abutment to subdivide the chamber. To further ease handling, some partitions have been mounted on rails for longitudinal movement in the chamber. In these constructions, the partitions are usually swung about hinges for movement between operative and loading positions.
In a partition system sold by ITW Insulated Products, two half-width partitions are mounted side-by-side on a single axle that is supported on each end by a trolley. Each trolley is movable along the length of a rail attached to one of the sidewalls adjacent the ceiling. In this system, the partitions are moved together along the rails to the desired longitudinal position. When the trailer is to be loaded or unloaded, the partitions are individually swung and latched to the ceiling. The half-width partitions are less weight and are thus easier to lift to the ceiling than a full width partition. Nevertheless, this system still requires the partitions to be moved together, and to be manually lifted and latched without mechanical assistance.
In U.S. Pat. No. 6,247,740, the partitions are individually mounted on separate axles, which are each mounted on a trolley. Each trolley moves along a rail extending across one of the sidewalls, and includes a hinge assembly that swings the partition either to the ceiling or the sidewall for loading or unloading of the trailer. The half-width partitions are more easily moved than full width partitions. However, the use of a single rail positioned along each of the sidewalls requires a relatively robust rail, trolley and axle assembly to prevent the partition from pulling from the wall. The trolley and axle assembly is also relatively complicated as compared to a single-axis hinge due to its ability to move to a loading position against the sidewall or ceiling. This system also includes lift ropes to ease lifting of the partitions when positioned along the ceiling. The ropes are hooked to anchors fixed to the sidewalls to hold the partitions in place during loading of the trailer. However, a taut segment of the lift rope extends downward along the sidewall when the partition is along the ceiling, thus risking being struck and damaged during loading of the goods into the trailer.
U.S. Pat. No. 6,626,625 discloses a partition system wherein half-width partitions are each separately mounted on a pair of trolleys movably attached to a plurality of spaced apart rails. One rail extends along each sidewall and two rails along the center of the ceiling. Each partition can be independently moved in a longitudinal direction and independently swung to the ceiling. Further, a lift rope is provided for lifting and lowering the partitions. The lift rope is fed through a control mechanism whereby a pivotal cam selectively holds and releases the rope as needed. However, since the pulleys and center rails are supported by the ceiling, the system can only be used in trailers constructed with ceilings able to support the necessary loads of the partition system. Moreover, operation of the cam via the lift rope requires a minimum clearance to laterally pull the rope for releasing the cam.
Further, goods transported in a refrigerated truck trailer are typically supported on pallets that are loaded and unloaded by fork lift trucks. The fork lift truck can at times mistakenly strike a partition set up to separate two partitioned areas. As the operators generally drive the fork lift trucks quickly, they can, at times, strike the partition with considerable force. In all current rail mounted partition systems, the partitions are fastened to the trolleys that are adapted to move along the rails. Such fastening can lead to breakage of the partitions when struck during loading or unloading of the goods.
SUMMARY OF THE INVENTION
The need exists for an improved partition system that provides the benefits sought by the industry without the previously concomitant disadvantages.
One object of the invention is to support the partition system solely by the sidewalls of the refrigerated chamber (e.g., a refrigerated truck trailer). In one preferred construction, a plurality of partial-width partitions are each mounted on a pair of rails for longitudinal movement, wherein the rails are part of a framework that is supported solely by the sidewalls of the trailer. In this way, an easy, reliable system is usable in refrigerated truck trailers that do not have load bearing ceilings.
Another object of the invention is to provide a lift assembly that is easy to use, reliable and economical. The inventive lift assembly eases movement of the partition to its loading position, forms no obstacles to loading of the goods, and requires only a few simple parts.
Another object of the invention is to releasably mount the partitions to trolleys supported by rails in the refrigerated chamber to avoid damage to the partition if it is struck during loading or unloading of the goods. The mounts permit the partition simply to disengage from the trolleys when struck with a certain force by a fork lift truck or other structure, thus, lessening the risk of damage and needed replacement.
In one preferred embodiment of the invention, the partition system includes two half-width partitions that are independently movable longitudinally in the trailer and independently swingable to the ceiling for easy movement to a loading position. Each partition is evenly supported by a pair of rails for easy movement without undue loading of the components. One rail extends along the sidewall and another along the center of the trailer for each partition. All of the rails are part of a framework that is supported solely by the sidewalls, i.e., with no loads placed on the ceiling. As a result, the system can be used in nearly all refrigerated trailers in use today.
A lift assembly in accordance with one embodiment of the invention includes a lift rope or other flaccid line, a pair of pulleys and a grip for holding the lift rope. A first pulley is generally aligned with the center of the partition. A second pulley guides the lift rope to a sidewall where it is less disruptive to the loading and unloading of goods. A grip for securing the lift rope is proximate the ceiling and avoids the formation of a taut rope segment along the sidewall. The grip has a simple construction that reliably holds the partition in the loading position as needed. In the preferred construction, the rails and lift assembly are each fully supported by the sidewalls without loading of the ceiling.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a partition system in accordance with the present invention with two partitions in a side-by-side abutting relation to subdivide the refrigerated chamber.
FIGS. 2 and 3 are partial views of the framework of the system.
FIG. 4 shows the interconnection of the partitions to the trolleys and the trolleys to the center rails in the operative positions of the partitions.
FIG. 5 shows a first pulley of the system.
FIG. 6 shows a second pulley and grip of the system.
FIG. 7 shows connection of the lift assembly to one of the partitions.
FIG. 8 shows lifting of one of the partitions by the lift assembly.
FIG. 9 is a top schematic view showing the system in the chamber.
FIG. 10 is a top schematic view showing the system in an alternative arrangement in the chamber.
FIG. 11 is a partial, exploded view of a partition mount.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A partition system 10 in accordance with the present invention subdivides a refrigerated chamber ( FIGS. 1–10 ). The chamber may be the interior of a truck trailer, railcar, cargo container or other similar structure. While the invention is further described in connection with a truck trailer for ease of illustration, it is not limited to such use.
Partition system 10 preferably includes a plurality of partial-width partitions 12 that can be arranged to subdivide interior chamber 14 of truck trailer 16 ( FIGS. 1 , 4 and 9 – 10 ). In a preferred embodiment, the partitions each extend laterally across half the width of the chamber. Two partitions 12 , then, can be placed in abutting relation to close the entire chamber and subdivide the chamber into two different partitioned areas or zones 18 . Nevertheless, three or more partitions can be fit in side-by-side abutment across the width of the chamber in wide chambers. Each partition preferably has an identical construction, though there could be differences if desired. Further, each partition is also preferably insulated to better keep the chamber portions at the different desired temperatures.
Partition system 10 includes rails 20 to facilitate longitudinal movement of the partitions ( FIGS. 1–4 and 6 – 8 ). Side rails 20 a extend along sidewalls 22 of trailer 16 proximal to ceiling 24 , and preferably are attached to the sidewalls via spaced brackets 25 secured by screws, rivets or the like. Cross bars 26 span the width of chamber 14 and also preferably attach to brackets 25 , but could attach to side rails 20 a . The number of cross bars to be used depends largely on the length of the chamber, the number of partitions used in the chamber, and/or the weight to be supported. In one preferred construction, three cross bars are provided—one adjacent front wall 27 , one adjacent rear doors 29 , and one centrally located. Center rails 20 b are secured to the cross bars along the centerline of trailer 16 preferably by connectors 31 . Rails 20 and cross bars 26 form a framework 28 that lies adjacent ceiling 24 and out of the way for loading and unloading of the trailer. Seal members 33 a , 33 b are preferably provided between rails 20 a , 20 b and ceiling 24 to better insulate one chamber portion 18 from another. Further, the entire framework is attached to and supported by the sidewalls 22 , preferably through brackets 25 , but could be attached to the sidewalls in other ways. For example, side rails 20 a and cross bars 26 could be directly fixed to sidewalls 22 or framework 28 could be secured to sidewalls 22 through the use of various other components or supports. Framework 28 forms the base of partition system 10 and supports the remaining components. As a result, all of the weight of system 10 is supported by sidewalls 22 , which is made to support loads in virtually all refrigerated truck trailers, without any loading of ceiling 24 . Partition system 10 is therefore usable in nearly every refrigerated truck trailer irrespective of whether the ceiling is of the load-bearing kind.
Rails 20 each preferably have a generally U-shaped configuration with side portions 30 , top portion 32 interconnecting side portions 30 , and bottom lips 34 extending inwardly from side portions 30 . Lips 34 extend only partially between side portions 30 so as to define a central slot 36 . Nevertheless, rails 20 could have other shapes so long as they movably support partitions 12 . Rails 20 a , 20 b also preferably have the same construction for ease and economics of manufacture, though different rail shapes could be used for the side and center rails. Further, the two center rails may be formed as a single integral member (not shown).
Trolleys 50 are movably supported on rails 20 and, in turn, support partitions 12 ( FIG. 4 ). In one preferred construction, trolleys include a narrow body 52 that extends through slot 36 in rails 20 . Rollers (not shown) are rotatably secured to the upper end of body 52 to ride along lips 34 , though skids or other arrangements could be provided to facilitate movement of the trolley along rail 20 . Screws 53 or other stops are provided in the ends of rails 20 a , 20 b to prevent inadvertent disconnection between trolleys 50 and rails 20 a , 20 b ( FIG. 3 ). An opening 56 is defined in a lower end of body 52 for receiving a pin 57 (e.g., one foot in length) that fits within hollow rod 58 ( FIGS. 1 and 4 ). In a preferred construction, pins 57 include flats 59 that cooperate with flats 61 in opening 56 ( FIG. 11 ). These flats provide increased support for holding pins 57 and the weight of partition 12 . Cotter pins 60 or the like are passed through pins 57 to hold them to trolleys 50 . If the partitions are struck by a fork lift truck, pallet or other structure, there is sufficient clearance for pins 57 to move. Specifically, pins 57 are forced to pivot along generally a horizontal plane about opening 56 , for example up to about 45°, toward the front of the trailer. This movement of pins 57 permits rod 58 to slide from one or both pins 57 and be separated from trolley(s) 50 to avoid damage to the partition. The partition can then be manually fit again onto the pins. Other releasable mounts could also be used.
Hinge plates 62 are rotatably mounted on each rod 58 for supporting partitions 12 . Each hinge plate 62 has a main plate portion 62 a bolted or otherwise secured to partition 12 and an eye 62 b that defines an aperture through which rod 58 is passed. In this way, partition 12 is freely rotatable about rod 58 . Of course, other trolley and hinge constructions could be used.
Each partition 12 preferably includes one or more handles 66 to facilitate their movement. In use, partitions 12 are pushed and/or pulled through chamber 14 by manually grasping one or more of the handles and causing the trolleys 50 to move along rails 20 . For each partition, one trolley is supported by one side rail 20 a and one other trolley is supported by one center rail 20 b . This provides an even support for the partition, which makes for an easy and smooth longitudinal movement of the partition. Handles 66 may also grasped to pivot partition 12 about rod 58 to and from its loading position. The partition may be manually lifted and latched in a loading position against or close to framework 28 or swung about rod 58 by a lift assembly 67 . In the loading position, chamber 14 can be loaded or unloaded without interference from partitions 12 . Of course, the partitions could have a variety of different constructions, including with or without handles, straps, or specific seal members.
To subdivide chamber 14 , two partitions are preferably placed in side-by-side abutment in the operative position ( FIGS. 1 , 4 and 9 – 10 ). Each partition preferably has a peripheral seal 70 to contact one sidewall 22 , ceiling 24 , an adjacent partition 12 , and floor 74 to block the passage of air from one portion to the next. Seal 70 is preferably sufficiently compressible to provide clearance for rails 20 without jeopardizing the seal needed to adequately subdivide the refrigerated chamber into portions capable of sustaining two different temperatures. Alternatively, the partitions could be shaped to accommodate the rails. Partitions 12 also preferably include straps 72 by which the adjacent partitions may be strapped together to form a more secure fit across the chamber.
Partition system 10 further preferably includes a lift assembly 67 for swinging each partition 12 from the operative position to the loading position, and vice versa ( FIGS. 5–8 ); although, a direct lifting and latching of the partitions by the operator without a lift assembly could be done. In the preferred construction, each lift assembly 67 includes a rope 82 or other flaccid member that includes a latch component 84 at the proximal end 86 . Latch 84 secures to ring 88 or other lock element fixed to partition 12 when the partition is to be lifted by lift assembly 80 . Ring 88 is preferably provided on one side of partition 12 , i.e., the lower side when stowed, though it could be provided on the other side or both sides of the partition.
A first or lifting pulley 90 is attached to one cross bar 26 , preferably the cross bar closest to rear doors 29 , approximately over the location of ring 88 on partitions 12 (i.e., roughly the center of the partition). Another first lifting pulley could be provided on other cross bars if more than one pair of partitions is included in the trailer. The first pulley is preferably located centrally of the partition. The first pulley is preferably mounted on a U-shaped base 89 to enable the pulley to freely orient itself as needed to connect to and lift the partition. A locking or second pulley 92 is also attached to the same cross bar 26 near side rail 20 a to a position out of the way of the goods. Second pulley 92 includes a grip or tackle 94 (e.g., as commonly used in sailing) that automatically holds the rope from moving in the release direction. Grip 94 is preferably integral with second pulley 92 but could be a separate member if desired. Grip 94 includes a pair of spring-biased, eccentric jaws 96 , preferably with serrations 98 , which are normally biased toward the closed position. In use, rope 82 passes around first pulley 90 , to and around second pulley 92 , and through jaws 96 of grip 94 . The jaws are pushed outward to an open position for passage of the rope. The jaws are biased toward the closed position to press against the rope. The jaws securely hold the rope in place and prevent slippage or release of the partition from the loading position. To release the partition to the operative position, rope 82 is pulled transversely out of grip 94 and the rope permitted to freely slide back over pulleys 90 , 92 under the weight of partition 12 . A stop, preferably in the form of a generally U-shaped bar, is set across from jaws 96 to prevent pulling the rope from pulley 92 . With the partition lowered, hook 84 is released from ring 88 . Partition 12 can then be moved longitudinally along rails 20 to the desired position.
In one embodiment, one or more partitions are mounted on each pair of rails 20 a , 20 b to subdivide chamber 14 into two or more chamber portions, e.g., chamber portions 18 a , 18 b ( FIGS. 1 and 9 ). In an alternative construction, a longitudinal partition or bulkhead 103 can be mounted along the centerline of the bulkhead to subdivide the bulkhead longitudinally as well as laterally to form multiple chamber portions, e.g., chamber portions 18 c , 18 d , 18 e ( FIG. 10 ). While longitudinal partitions 103 are preferably of conventional design and held in place by friction, they could be fabricated for suspension from framework 28 . Longitudinal partitions 103 ′ can also be used with partitions 12 to form a z-shaped partition border, which can be useful when an odd number of pallets are loaded into the refrigerated chamber.
The above discussion concerns the preferred embodiments of the present invention. Various other embodiments as well as many changes and alterations may be made without departing from the spirit and broader aspects of the invention as claimed. For example, the use of a framework of rails and cross members supported solely by the sidewalls of the chamber could be used with other partition systems. Also, the lift assembly and the use of mounts that permit release of the partitions when struck could be effectively used with many different partition systems, including those with single axles or full width partitions.
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A partition system includes partial-width partitions that are independently movable longitudinally in the trailer and independently swung to the ceiling for easy stowing. Each partition is evenly supported by a pair of rails for easy movement without undue loading of the components. One rail extends along the sidewall and another along the center of the trailer for each partition. All of the rails are part of a framework that is supported solely by the sidewalls with no loads placed on the ceiling. A lift assembly includes a lift rope, a pair of pulleys and a grip for holding the lift rope. A first pulley is generally aligned with the center of the partition to avoid substantial side loading on the pulleys during lifting and lowering of the partition. A second pulley guides the lift rope to a sidewall where it is less disruptive to the loading and unloading of goods. The grip is proximate the ceiling and avoids the formation of a taut rope segment along the sidewall. The grip has a simple construction that reliably holds the partition in the loading position as needed.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a centerless grinding machine for grinding workpieces mainly by using a super abrasive grinding wheel and with an ultra precision grinding operation.
2. Description of the Prior Art
Typically a centerless grinding machine is comprised of a grinding wheel, a regulating wheel, and a blade which is disposed between the two wheels for supporting a workpiece, whereby the workpiece supported by the blade and regulating wheel is ground to a desired dimension by the grinding operation of the grinding wheel facing the regulating wheel.
In such a centerless grinding machine, the grinding wheel is fixed to the rotational spindle through a tapered flange and the like, and is rotatively driven by a pulley mounted on one end of the rotational spindle. Further, when the grinding wheel becomes worn out, the position of a table provided for the grinding wheel is compensated by the amount of the wear for the accurate grinding to be effected. The guide ways for the grinding wheel table are formed by a hydrodynamic guide or low friction rolling guide way, or hydrostatic guide way. Such a machine which is manufactured for general purposes may also be applied to the grinding operation by the super abrasive grinding wheel.
In a grinding operation, the machining accuracies and efficiencies for a workpiece is mainly affected by the degree of accuracies and rigidities of the workpiece support and drive system and that of the grinding wheel including its rotational spindle.
When a large dimensioned super abrasive grinding wheel is to be used in a centerless grinding machine, and it is necessary to true the grinding wheel with accuracy, a special trueing machine provided apart from the grinding machine has to be used. In removing from the trueing machine the grinding wheel which has been trued and mounting it again on the grinding machine, any changes in accuracies should not occur that would increase the peripheral run-out of the wheel due to the mounting error of the wheel assembly in its transfer. However, in the structure of the conventional grinding machine, it is not possible to achieve the accuracy of the grinding wheel which satisfies the requirement to perform an ultra precision grinding operation, when the grinding wheel or grinding wheel unit which has been trued outside of, or apart from, the grinding machine is mounted again on the grinding machine.
Furthermore, in order to control the workpiece dimension to a high accuracy, it is necessary to accurately control the position of the grinding wheel tables. When a hydrodynamic guideway is used for the guideway for positioning the table, the accurate positioning of the wheel table can not be accomplished due to the influence of frictional force. In the structure which makes use of a low friction guideway, such as a rolling guideway and the like, there is such a defect that chatter vibrations tend to occur because of a low rigidity in the guiding direction, and this guideway is not appropriate for a high precision and efficient grinding.
SUMMARY OF THE INVENTION
Accordingly, a primary object of the present invention is to provide a centerless grinding machine which is capable of ensuring high rigidity and space saving construction of a grinding wheel unit and regulating wheel unit and of effecting the reliable reproducibility of the accuracies of the grinding wheel after it is dressed, by providing each of the units on a rotational sleeve supported by a hydrostatic bearing means on a spindle.
Another object of the present invention is to provide a centerless grinding machine which is capable of fine positioning of the corresponding wheel table and improvement in accuracies and efficiencies in grinding a workpiece, by providing a structure in which a pre-load is applied through a hydrostatic bearing onto a hydrodynamic sliding guide way which serves as a feed guide way of the grinding wheel table and regulating wheel table, and also by providing a servo mechanism which is operable to detect any frictional forces generated on the feed guide way and compensate for such frictional forces.
According to the present invention, there is provided a centerless grinding machine comprising a grinding wheel, a regulating wheel, tables each supporting a corresponding wheel, a blade for supporting a workpiece, a bed on which these elements are provided, a spindle fastened at the both ends to the associated table supporting the corresponding wheel, a rotational sleeve supported at the inner peripheral surface by hydrostatic radial bearing means, and thrust bearing means on the spindle and provided at the outer periphery with said grinding wheel and regulating wheel and at one end with a rotatively driving element, means to apply through a hydrostatic bearing a uniform pre-load to a hydrodynamic sliding guide way which serves as a feed guide way for guiding the corresponding table, and a servor mechanism which is operable to compensate for frictional forces generated on said feed guide way.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings show a preferred embodiment of a centerless grinding machine in accordance with the present invention, wherein:
FIG. 1 is a front elevational view of the grinding machine;
FIG. 2 is a longitudinal cross sectional view of a grinding wheel sleeve and grinding wheel table, viewed from the side of the grinding wheel;
FIG. 3 is a cross sectional view taken along the line X--X shown in FIG. 2;
FIG. 4 is a fragmentary longitudinal cross sectional view of a table positioning portion of the grinding wheel table;
FIG. 5 is an explanatory schematic and partly cross-sectional view of a device for detecting a force applied to a feed screw shaft; and
FIG. 6 is a longitudinal cross-sectional view showing the arrangement of a guideway of the grinding wheel table and a bed.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
An embodiment of a centerless grinding machine in accordance with the present invention will now be described in detail with reference to the accompanying drawings.
A centerless grinding machine A is mainly comprised of a bed 1, a grinding wheel 2, a regulating wheel 3, and a blade 4 for supporting a workpiece W. The workpiece W is supported in a V-shaped or wedged void space defined by the regulating wheel 3 and the surfaces of the blade 4. A grinding wheel table 5 for supporting the grinding wheel 2 is positioned by performing the table positioning movement, and the outer periphery of the supported workpiece W is ground by the grinding wheel 2 of a grinding wheel sleeve U (FIG. 2) supported by a hydrostatic radial bearing means and a thrust bearing means on a spindle 20 which is fixed on the grinding wheel table 5.
The blade 4 is provided on a workrest 8 mounted on a workrest mounting base 7, which is disposed between the grinding wheel table 5 and a regulating wheel table 6, and which is fixed to the bed 1.
The grinding wheel sleeve U is supported by the hydrostatic radial bearing means and thrust bearing means on the spindle 20. This spindle 20 is fixed to the grinding wheel table 5 by placing the spindle in semi-circular supporting portions 5a and 5b provided on the upper surface of the grinding wheel table 5 so as to be received in these portions, covering the thus placed spindle with semicircular supporting portions 9a and 9b provided on the lower surface of a cover 9, and fastening the above elements by use of screw bolts. The grinding wheel table 5 is guided on the guideways provided below the table 5 and is operated by rotation of a driving motor 10 through a feed screw shaft 11, thus being able to move in the left or right direction as viewed in FIG. 1.
The grinding wheel 2 is rotatively driven by a driving motor (not shown), which is provided separately apart from the bed 1, through a belt 12 and intermediate shafts.
Reference number 13 designates a normal grinding wheel dressing trueing device for trueing the surface of a general purpose grinding wheel (not for super abrasive wheels), which is provided on the machine A on the side of the grinding wheel 2.
A stationary spindle for the regulating wheel 3 is mounted on the regulating wheel table 6 in the same manner as the spindle 20 for the grinding wheel, such that the stationary spindle is received in semi-circular supporting portions provided on the upper surface of the regulating wheel table 6, is covered with semi-circular supporting portions provided on the lower surface of a cover 15, and is fixed in place by screw bolts.
The regulating wheel table 6 is guided on the feed guide ways provided below the table 6 and is operated by a handle 16, or rotation of a feed motor, through a feed screw, thus being able to move in the left or right direction as viewed in FIG. 1. Reference number 17 designates a trueing device for trueing the surface of the regulating wheel 3, while reference number 18 designates a driving motor for the regulating wheel 3. The regulating wheel 3 is rotatively driven by this motor 18 through a reduction unit and intermediate shafts.
FIG. 2 illustrates a grinding wheel sleeve and a grinding wheel, and assists in explaining the arrangement of these members. The spindle 20 is fixed to the grinding wheel table 5, as described above, by placing left and right ends 20a and 20b of the spindle 20 respectively in the semi-circular supporting portions 5a and 5b provided on the grinding wheel table 5, respectively covering the upper portions of the both ends of the spindle 20 with the semi-circular supporting portions 9a and 9b of the cover 9, and fastening them by screw bolts. This spindle 20 supports the grinding wheel sleeve U by the hydrostatic radial bearing means and thrust bearing means provided on the spindle 20 which is stationary, and the grinding wheel sleeve U is arranged on the spindle 20 within the grinding wheel table 5. The grinding wheel sleeve U comprises a rotational sleeve 21, and the grinding wheel 2 which is fitted on the outer periphery of the rotational sleeve 21 and fixed thereto by fastening a screw bolt 23 in the axial direction through a movable flange 22. The rotational sleeve 21 is provided at one end thereof with a rotatively driving pulley portion 24 on which the belt 12 is disposed. The inner peripheral surface 21a of the rotational sleeve 21 serves as a rotational hydrostatic radial bearing surface, while the left end surface 21b of the rotational sleeve 21 serves as the reference surface for mounting thrust bearing plates 25 and 26. With this arrangement, the rotational sleeve 21 is rotatively driven by the belt 12 while the spindle 20 is kept stationary. The rotatively driving pulley portion 24 is provided with a labyrinth seal portion S for preventing penetration of any grinding fluid. The spingle 20 has near its left end a projecting thrust flange 20c which constitutes the thrust bearing means. The thrust flange 20c is provided on either of the sides thereof with an annular thrust pocket 27 or 28.
Pressurized oil is supplied to these thrust pockets 27 and 28 in the following manner. Pressurized oil is supplied from a supply port 29 to the thrust pocket 29 through an accommodated filter 30, distribution pipe line 31, and restrictor 32. The thrust pocket 27 as well as radial arranged pockets 33 of the spindle 20 is supplied with pressurized oil in the same manner. Oil flowing out of the bearing means is discharged from drain ports 38 and 39 to the outside of the machine through drain pipe lines 34, 35, 36 and 37.
Referring to FIG. 3, the stationary spindle 20 is provided on the outer periphery with radial pockets 33 which comprise two pairs of pockets arranged axially. Each radial pocket 33 is supplied with pressurized oil from supply ports 29 and 40 through filters 30 and 41, pipe lines 31 and 42 and an orifice. Oil flowing out from the bearing surface clearance between the outer periphery of the spindle 20 and the inner periphery 21a of the rotational sleeve 21 is allowed to flow into internal annular gaps 43, 44 and 45 and discharged from the discharge ports 38 and 39 through oil discharge pipe lines 46, 47, 48, 36 and 37. Oil seals 49 and 50 are disposed such as to seal the annular gaps for discharge of oil, thus preventing any oil from escaping outside.
Thus, the hydrostatic radial bearing means is formed between the outer periphery of the stationary spindle 20 and the inner periphery of the rotational sleeve 21 of the grinding wheel sleeve U, thereby supporting the rotational sleeve 21 on the stationary spindle 20 in a non-contact manner and thus determining the position of the former.
The structure for causing the table positioning movement of the grinding wheel table 5 will be described with reference to FIG. 4. A feed screw nut 51 an one end of a feed screw shaft 11, which is screwed into the feed screw nut 51, are mounted on the rear side surface of the grinding wheel table 5 at a height corresponding to that of the center of the grinding wheel 2. The nut 51 is composed of a double nut onto which a certain pre-load is applied so that there will be residual clearance. The other end of the feed screw shaft 11 is supported in a non-contact manner by a hydrostatic thrust bearing 53 and a hydrostatic radial bearing 54 which are provided within a bracket 52 mounted on the bed 1. An internal gear coupling plate 55 is mounted on the end face of the feeding screw shaft 11, and this plate 55 is engaged with an external gear plate 56 provided on the driving side of the machine. The external gear plate 56 is connected to the driving motor 10 through a reduction unit, while the internal gear coupling plate 55 is arranged to be movable in the axial direction without transmitting any thrust load.
Accordingly, the feed screw shaft 11 is rotated by the driving motor 10 through other associated elements, whereby the grinding wheel table 5 can be moved in the left or right direction. At this time, frictional force is generated on the feed guide ways provided below the grinding wheel table 5, while a thrust force corresponding to this frictional force is applied to various components of the feed system.
When a large frictional force is generated, the screw mounting bracket 52 becomes elastically deformed in the left or right direction and this causes a reduction in the positioning accuracy. This phenomenon also leads to incorrect positioning when the feeding direction is inverted.
In the event that the screw mounting bracket 52 is deformed, it is impossible to move the grinding wheel table 5 by an amount corresponding to the rotational angle of the screw shaft.
In order to avoid such problems, a hydraulic actuator B is provided in accordance with the present invention below the grinding wheel table 5 at a location corresponding to the position of the feed guide ways. In this hydraulic actuator B, a piston rod 57 is fixed at one end to the grinding wheel table 5 and is slidably inserted into a cylinder 59 which is fixed to an actuator mounting bracket 58, and this bracket 58 is, in turn, fixed to the bed 1. A servo valve 60 is also provided on the hydraulic actuator B so as to supply selectively the output pressure oil to a pressure chamber 59a or 59b.
The design according to the present invention is, therefore, such that the force applied to the feed screw shaft 11 is detected, the hydraulic actuator B is made to generate the force required for moving the grinding wheel table 5, and the servo valve 60 is made to operate so as to constantly minimize the force applied to the screw shaft 11, thus eliminating deformation of the screw mounting bracket 52, and thereby enabling movement of the grinding wheel table 5 by an amount corresponding to the rotational angle of the screw shaft. Such operation concerning the force applied to the feeding screw shaft 11 will be explained with reference to FIG. 5.
The pressure difference between the opposite pockets of the hydrostatic thrust bearing 53 is proportional to the force applied to the feeding screw shaft 11. Therefore, this pressure difference is electrically detected by a pressure difference sensor 68, and a correction signal is supplied to the servo valve 60 through servo amplifier 69.
FIG. 6 shows the arrangement of a wheel table and the guide ways on the bed 1. Guide ways 1a which extend in the horizontal direction are provided on the upper surface of the bed 1, while the lower surface of the grinding wheel table 5 has guide ways 5c which cooperate with guide ways 1a to form a hydrodynamic sliding guide way. The grinding wheel table 5 has on a central lower portion thereof a T-shaped protrusion 5d. Left and right horizontal portions of this protrusion 5d are brought into facing relationship with a pair of protrusions 1b provided on the central portion of the bed 1.
Hydrostatic pockets 61 are provided on the horizontal portion of the protrusion 5d at locations facing the corresponding protrusions 1b of the bed 1. These pockets 61 are supplied with pressurized oil from a supply port 63 formed in a terminal 62, which is mounted on the grinding wheel table 5, through a restrictor 64 and a pipe line 65. Pressure within the pockets 61 thus acts to urge the grinding wheel table 5 in the downward direction, and thus serves to apply an additional pre-load to the hydrodynamic sliding guide ways 5c.
The terminal 62 has hydrostatic pockets 66 to which pressurized oil is supplied through an orifice 67. These pockets 66 and the mating lateral surface of the bed 1 form a hydrostatic bearing. That is, the reaction force of the pressure within the pockets 66 acts on grinding wheel table 5 to urge vertical guide way 5e thereon toward a vertical guide way 1c on the bed 1, and thus serves to apply a pre-load to the hydrodynamic sliding guide ways formed by the vertical guide ways 5e and 1c.
With this arrangement, the pre-load can be adjusted with ease by varying the supply pressure of oil supplied from the supply port 63.
A plurality of such pockets for applying pre-load are provided in the direction in which the table 5 is guided, so that the pre-load can be uniformly applied.
Therefore, in the above-mentioned constitution of the present invention, a highly rigid and space saving construction of a grinding wheel and a regulating wheel is obtained and it is possible to prevent the mounting error from being caused due to transfer of the wheels for trueing outside of the machine. Further, the fine positioning of the wheel table can be accurately effected. Furthermore, the precision and efficiency in working of the workpiece can be increased. In addition, the construction is simple.
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A centerless grinding machine comprising a grinding wheel on a rotational sleeve supported by a hydrostatic bearing means on a stationary spindle fixed to a grinding wheel table, a regulating wheel supported by a hydrostatic bearing on a spindle fixed to a regulating wheel table, and a blade for supporting a workpiece. Both wheel tables supporting the corresponding wheel are guided along a hydrodynamic sliding guide way to which a uniform pre-load is applied by hydrostatic bearings, and a servo mechanism is provided to compensate for frictional forces generated on the feed guide way, whereby it is possible to accomplish fine positioning of the corresponding wheel table and to grind the outer periphery of the workpiece with high precision and efficiency.
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The present invention relates to 2,5-disubstituted thiophene derivatives, and more particularly, to 2-aryloxy-5-alkansulfonamido-thiophenes which are pharmacologically active in alleviating inflammation, asthma, arthritis, hypersensitivity, myocardial ischemia and dermatological conditions, such as, psoriasis and dermatitis, and gastrointestinal inflammatory conditions, such as, inflammatory bowel syndrome.
BACKGROUND OF THE INVENTION
Non-steroidal Antiinflammatory drugs (NSAIDs) such as indomethacin, naproxen, piroxicam, diclofenac and the like have been shown to alleviate inflammation. Their mode of action has been generally attributed to their ability to inhibit the enzyme cyclooxygenase (CO), a key enzyme in the arachidonic cascade, which attenuates the biosynthesis of various prostaglandins. The prostaglandin end-products of the cyclooxygenase pathway are responsible for many of the early signs of inflammation including increases in vascular permeability leading to edema, hyperalgesia and pyrexia.
The other major pathway of arachidonic acid (AA) metabolism is the lipoxygenase pathway. Lipoxygenase products of arachidonate metabolism such as the leukotrienes (LTs), hydroxyeicosatetraenoic acids (HETEs) and hydroperoxyeicosatetraenoic acid (HPETEs) have been implicated in disease states including acute and chronic inflammation, arthritis, allergic and other hypersensitivity disorders, and various dermatological, cardiovascular, hyperalgesic and gynecological disorders. In particular, the LTs which are the products of 5-lipoxygenase (5-LO) catalyzed oxygenation of AA participate in a variety of chronic and acute inflammatory diseases. Leukotriene B 4 (LTB 4 ), a key LT product, is believed to play a role in chronic inflammatory conditions such as rheumatoid arthritis. LTB 4 is chemotactic to inflammatory cells and helps to contribute to the chronic influx of leukocytes into the synovial fluid which eventually results in joint erosion.
Pharmacologically active compounds that can inhibit both enzyme pathways at similar concentrations have the potential to provide more complete relief for patients suffering from arthritis and inflammatory, hypersensitivity, dermatological, cardiovascular, gastrointestinal, ocular and gynecological disorders. An example of such a compound is the antiinflammatory agent 3- 5-(4-chlorophenyl)- 1-(4-methoxyphenyl)-3-pyrazolyl!-N-hydroxy-N-methyl pro-panamide, tepoxalin, which is one of a series of 1,5-diaryl-3-substituted pyrazoles disclosed in U.S. Pat. Nos. 5,164,381 and 4,826,868 (Wachter & Ferro). Other 1,5-diaryl-pyrazoles which act as dual 5-LO and CO inhibitors and possess antiinflammatory activity are described in U.S. Pat. Nos. 5,051,018; 5,242,940; 5,298,521 and 5,387,602.
Recently, the cyclooxygenase enzyme was shown to exist as two isoforms: COX-1 and COX-2 (Medicinal Chemistry Research, Vol. 5, No. 5, pp 319-408 (1995)!. COX-1, which is constituitively expressed, is present in tissues such as stomach, gut or kidney where prostaglandins have a cytoprotective effect in maintaining normal physiological processes. COX-2, which is induced or stimulated by inflammatory or mitogenic stimuli, is the probable primary target in inflammatory disease states and its selective inhibition vs COX-1 provides an opportunity to inhibit the inflammatory, pyretic and thrombogenic effects of prostaglandins while avoiding the ulcerogenic and nephrotoxic side effects that result from non-selective inhibition.
The present invention describes compounds that are dual inhibitors of both the 5-LO and COX-2 enzymes. In addition, these compounds selectively inhibit COX-2 as opposed to COX-1, and possess the ability to reduce inflammation without the side effects on the gastric mucosa and kidney which are associated with previous NSAID therapy.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 graphically depicts the effects of the compound of Example 1 on ex vivo LTB 4 production in dogs five hours following oral administration of compound.
SUMMARY OF THE INVENTION
The present invention provides 2,3 and 2,5-disubstituted thiophenes, their use and a method of their synthesis. The compounds of this invention are pharmacologically active in alleviating inflammation and inhibit the cyclooxygenase pathway primarily via COX-2, the lipoxygenase pathway, or preferably both pathways.
In particular, the invention provides a thiophene derivative of general formula I ##STR2## Wherein, R 2 is CF 3 , C 1 -C 10 alkyl, or phenyl;
X is O, S, or CH 2 ; and
R is aryl, C 1 -C 10 alkyl, or C 3 -C 8 cycloalkyl wherein aryl refers to a phenyl or naphthyl moiety which may be substituted by one or more of the following: halogen, CF 3 , C 1 -C 4 alkyl, alkoxy, alkylthio, or alkylsulfonyl; and the pharmaceutically acceptable salts, esters and pro-rug forms thereof.
Preferred compounds of the invention are encompassed by the following general formula II. ##STR3## Wherein, R 1 is halogen, CF 3 , C 1 -C 4 alkyl, alkoxy, alkylthio, or alkylsulfonyl.
The present invention also contemplates a pharmaceutical composition that comprises an antiinflammatory amount of an above-described substituted thiophene compound dispersed in a pharmaceutically acceptable carrier. The dose may be administered by topical, oral parenteral or aerosol routes. In preferred practice, an amount of those compounds of the invention capable of inhibiting both the cyclooxygenase and the lipoxygenase pathways are utilized in the composition when the composition is administered to a mammal.
Further contemplated is a method for alleviating inflammation in a mammal exhibiting an inflammatory condition. The method comprises administering to such mammal a pharmaceutical composition that includes as active ingredient an effective amount of a compound of the present invention in association with a pharmaceutically acceptable carrier for topical, oral, parenteral or aerosol administration.
DETAILED DESCRIPTION OF THE INVENTION
The preferred 2,5-disubstituted thiophene compounds of the invention in which X=O can be prepared according to Scheme 1. ##STR4##
Treatment of 2-Nitro-5-bromothiophene A with the appropriately substituted phenol B in DMF with a base such as potassium carbonate gives the corresponding 2-nitro-thiophene ether C. The ether C is dissolved in acetic acid and treated with acetic anhydride and Fe powder to yield the corresponding acetamide D. The acetamide is dissolved in an inert solvent such as tetrahydrofuran, cooled to -78° and treated with a base such as lithium diisopropylamide followed by treatment with methanesulfonyl chloride. The intermediate disubstituted amino derivative is evaporated to dryness and redissolved in ethanol and then treated with ammonium hydroxide to give the desired methansulfonamide E.
To prepare the 2,5-disubstituted thipohene compounds of the invention where R is alkyl or cycloalkyl, the appropriately alkanol or cycloalkanol compound can be substituted for the phenol B in the foregoing reaction scheme.
The 2,5-disubstituted thiophene compounds of the invention in which X=S can be prepared according to Scheme 2. ##STR5##
The compounds of general structure F were synthesized from compound A according to the method described above utilizing the appropriate thiol in place of a phenol. Conversion of compounds F to compounds H is accomplished following a similar procedure as that outlined in Scheme 1.
The 2,5-disubstituted thiophene compounds of the invention in which X=CH 2 can be prepared according to Scheme 3.
Scheme 3
Treatment of 5-Nitrothiophene-2-carboxaldehyde I with an appropriately substituted arylmagnesium bromide in an inert solvent such as THF yields the alcohol J. Deoxygenation of the alcohol is carried out with triethylsilane and BF 3 etherate to give compound K. Conversion of the nitro functionality in K to the methanesulfonamido group in M is carried out as described for for the corresponding analogs in Scheme 1.
The 2,5disubstituted thiophene compounds of the invention in which X=a single bond can be prepared according to Scheme 4. ##STR6##
Treatment of compound A with a Pd(0) catalyst such as tetrakis(triphenylphos- phine)palladium(0) in a solvent such as toluene in the presence of an arytboric acid represented by N yields the biaryl coupling product O. Conversion of the nitro group of O to methansulfonamide Q is carried out as described for Scheme 1.
The 2,5disubstituted thiophene compounds of the invention in which R 2 =C 2 -C 10 alkyl and phenyl can be prepared according to Scheme 5. ##STR7## Acetamide D, the synthesis of which was described in Scheme 1, is dissolved in an inert solvent such as tetrahydrofuran, cooled to -78° and treated with a base such as lithium diisopropylamide followed by treatment with the appropriate alkyl or arylsulfonyl chloride. The intermediate disubstituted amino derivative is evaporated to dryness and redissolved in ethanol and then treated with ammonium hydroxide to give the desired sulfonamide R.
2,3-disubstituted thiophene compounds of the invention in which X=O can be prepared according to Scheme 6. ##STR8##
2-Nitro-3-bromothiophene is dissolved in a solvent such as DMF and treated with a base such as potassium carbonate and an appropriately substituted phenol at a temperature of 80° C. to give the aryl ether T. The nitro ether is reduced with tin powder in concentrated HCI at 60° C. to yield the tin double salt U. The salt is dissolved in pyridine, cooled to 0° C. and treated with methanesulfonyl chloride to give the 2,3-disubstituted thiophene methanesulfonamide V.
The foregoing reactions are performed in a solvent appropriate to the reagents and materials employed and suitable for the transformation being effected. It is understood by those skilled in the art of organic synthesis that the various functionalites present on the molecule must be consistent with the chemical transformations proposed. This will frequently necessitate judgment as to the order of synthetic steps, protection of reactive groups, and selection of reaction conditions. Reaction conditions compatible with the substituents employed will be apparent to one skilled in the art, as will be the selection of protecting groups where needed.
From formula 1 it is evident that some of the compounds of the invention may have one or more asymmetrical carbon atoms in their structure. It is intended that the present invention include within its scope the stereochemically pure isomeric forms of the compounds as well as their racemates. Stereochemically pure isomeric forms may be obtained by the application of art known principles. Diastereoisomers may be separated by physical separation methods such as fractional crystallization and chromatographic techniques, and enantiomers may be separated from each other by the selective crystallization of the diastereomeric salts with optically active acids or bases or by chiral chromatography. Pure stereoisomers may also be prepared synthetically from appropriate stereochemically pure starting materials, or by using stereospecific reactions.
Suitable pharmaceutical salts are those of inorganic or organic acids, such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, succinic acid, oxalic acid, malic acid and the like. Suitable salts are also those of inorganic or organic bases, such as KOH, NaOH, Ca(OH) 2 , AI(OH) 3 , piperidine, morpholine, ethylamine, triethylamine and the like.
Also induced within the scope of the invention are the hydrated forms of the compounds which contain various amounts of water, for instance, the hydrate, hemihydrate and sesquihydrate forms.
The substituted thiophene compounds of the invention are capable of inhibiting the lipoxygenase enzyme pathway and/or the cycolooxygenase 2 (COX-2) enzyme pathway to achieve the desired pharmacological result. In preferred practice, the 1,5 -disubstituted thiophene compound of the pharmaceutical composition is capable of inhibiting both the cyclooxygenase and the lipoxygenase enzyme pathways in the amount in which the compound is present in the composition, when the composition is administered as a unit dose in the appropriate mammal to be treated.
When the compounds are employed for the above utility, they may be combined with one or more pharmaceutically acceptable carriers, e.g., solvents, diluents, and the like, and may be administered orally in such forms as tablets, capsules, dispersible powders, granules, or suspensions containing for example, from about 0.5% to 5% of suspending agent, syrups containing, for example, from about 10% to 50% of sugar, and elixirs containing, for example, from about 20% to 50% ethanol, and the like, or parenterally in the form of sterile injectable solutions or suspensions containing from about 0.5% to 5% suspending agent in an isotonic medium. These pharmaceutical preparations may contain, for example, from about 0.5% up to about 90% of the active ingredient in combination with the carrier, more usually between 5% and 60% by weight.
Compositions for topical application may take the form of liquids, creams or gels, containing a therapeutically effective concentration of a compound of the invention admixed with a dermatologically acceptable carrier.
In preparing the compositions in oral dosage form, any of the usual pharmaceutical media may be employed. Solid carriers include starch, lactose, dicalcium phosphate, microcrystalline cellulose, sucrose and kaolin, while liquid carriers include sterile water, polyethylene glycols, non-ionic surfactants and edible oils such as corn, peanut and sesame oils, as are appropriate to the nature of the active ingredient and the particular form of administration desired. Adjuvants customarily employed in the preparation of pharmaceutical compositions may be advantageously included, such as flavoring agents, coloring agents, preserving agents, and antioxidants, for example, vitamin E, ascorbic acid, BHT and BHA.
The preferred pharmaceutical compositions from the standpoint of ease of preparation and administration are solid compositions, particularly tablets and hard-filled or liquid-filled capsules. Oral administration of the compounds is preferred.
These active compounds may also be administered parenterally or intraperitoneally. Solutions or suspensions of these active compounds as a free base or pharmacological acceptable salt can be prepared in water suitably mixed with a surfactant such as hydroxypropyl-cellulose. Dispersions can also be prepared in glycerol, liquid polyethylene glycols and mixtures thereof in oils. Under ordinary conditions of storage and use, these preparations may contain a preservative to prevent the growth of microorganisms.
The pharmaceutical forms suitable for injectable use include sterile aqueous solutions or dispersions and sterile powders for the extemporaneous preparation of sterile injectable solutions or dispersions. In all cases, the form must be sterile and must be fluid to the extent that easy syringability exists. It must be stable under the conditions of manufacture and storage and must be preserved against the contaminating action of microorganisms such as bacteria and fungi. The carrier can be a solvent or dispersion medium containing, for example, water, ethanol, polyol (e.g., glycerol, propylene glycol and liquid polyethylene glycol), suitable mixtures thereof, and vegetable oils.
The effective dosage of active ingredient employed may vary depending on the particular compound employed, the mode of administration and the severity of the condition being treated. However, in general, satisfactory results are obtained when the compounds of the invention are administered at a daily dosage of from about 0.01 mg/kg to about 500 mg/kg of animal body weight, preferably given in divided doses two to four times a day, or in sustained release form. For most large mammals the total daily dosage is from about 10 to about 2000 milligrams, preferably from about 100 mg to 1000 mg. Dosage forms suitable for internal use comprise from about 100 mg to 500 mg of the active compound in intimate admixture with a solid or liquid pharmaceutically acceptable carrier. This dosage regimen may be adjusted to provide the optimal therapeutic response. For example, several divided doses may be administered daily or the dose may be proportionally reduced as indicated by the exigencies of the therapeutic situation. Veterinary dosages correspond to human dosages with the amounts administered being in proportion to the weight of the animal as compared to adult humans.
The production of the above-mentioned pharmaceutical compositions and medicaments is carried out by any method known in the art, for example, by mixing the active ingredients(s) with the diluent(s) to form a pharmaceutical composition (e.g. a granulate) and then forming the composition into the medicament (e.g. tablets).
EXAMPLES
Method 1: General Procedure for the Synthesis of Compounds E ##STR9##
2-Nitro-5bromothiophene (1 equivalent) is dissolved in dimethylformamide (3 mL per mmol) and to the resulting solution is added the appropriately substituted phenol (1 equivalent) and potassium carbonate (2 equivalents). This mixture is stirred at 70° C. for 4-8 hours and then poured into water and the crude solid filtered and washed with water to give the intermediate 2-Nitro-5-phenoxy-thiophene.
The above substituted 2-nitro-5-phenoxythiophene (1 equivalent) is dissolved in acetic acid (3 mL per mmol) and treated with acetic anhydride (1 equivalent) and iron powder (4 equivalents). The resulting mixture is heated at 80° C. for 4-8 hours and then poured into water and the crude solid filtered and purified via chromatography on silica gel to yield the desired 2-acetamido-5-phenoxy thiophenes.
The 2-acetamido-5-phenoxy thiophene (1 equivalent) is dissolved in THF (7.5 mL per mmol) and cooled to -78° C. Lithium diisopropylamide (1.1 equivalents) is added and the solution stirred for an additional ten minutes before methanesulfonyl chloride (1.1 equivalents) is added. After 1-2 hours the mix is evaporated in vacuo and redissolved in ethanol. Concentrated ammonium hydroxide (0.5 mL per mmol) is added and after 30-60 minutes the mixture is again evaporated in vacuo. The residue is partitioned between methylene chloride and 1N HCI. The organic layer is washed with water, dried over magnesium sulfate and concentrated in vacuo. The resulting 2-methane-sulfonamido-5-phenoxy thiophene is purified via silica gel column chrom-atography eluted with hexane-ethyl acetate 1:1.
Example 1
A specific procedure for the synthesis of:
N- (4-fluoro)-5-phenoxythien-2-yl!methanesulfonamide (1) ##STR10##
2-Nitro-5-bromothiophene (2.97 g, 14.2 mmol) was dissolved in dimethyl-formamide (40 mL). To this was added 4-fluorophenol (1.59 g, 14.2 mmol) and potassium carbonate (3.92 g, 28.4 mmol). This was stirred at 70° C. for 5 hours after which time the mix was poured into water and the crude solid was filtered and washed with water to give 2-Nitro-5(4-fluoro)phenoxythiophene 2.67 g (78%), mp=69°-70° C.
2-Nitro-5-(4-fluoro)phenoxythiophene (2.44 g, 10.2 mmol) was dissolved in acetic acid (20 mL). To this was added acetic anhydride (20 mL) and iron powder (2.28 g, 40.8 mmol). This was stirred at 80° C. for 5 hours. The mix was then poured into water and the crude solid was filtered and purified on a silica gel column eluted with ethyl acetate-hexane 1:1 giving 1.10 g (43%) of N- (4-fluoro)-5-phenoxythien-2-yl!acetamide, mp=116.8-117.5° C.
N- (4-fluoro)-5-phenoxythien-2-yl!acetamide (1.0 g, 3.98 mmol) was dissolved in tetrahydrofuran (30 mL) and cooled to -78° C. Lithium diisopropylamide (3.0 mL of a 1.5M sol'n) was added and this was stirred for an additional ten minutes before methanesulfonyl chloride (0.35 mL, 4.5 mmol) was added. After one hour the mix was evaporated in vacuo and redissolved in ethanol. Concentrated ammonium hydroxide (2 mL) was added and after 30 minutes the mixture was again evaporated in vacuo. The residue was partitioned between methylene chloride and 1N HCI. The organic layer was washed with water, dred over magnesium sulfate and concentrated in vacua. The product was purified using silica gel column chromatography eluted with hexane-ethyl acetate 1:1 giving N- (4-fluoro)-5-phenoxythien-2-yl!methanesulfon-amide, 0.79 g (69%), Mp 94°-95° C. 1 HNMR (CDCI 3 ) ∂3.08 (s, 3H, CH 3 ), 6.27 (d,1H, Th H), 6.72 (d,1H, Th H), 7.07 (m, 4H, Ar). CIMS (m/e) 288 (MH + ). Anal Calcd for C 11 H 10 FNO 3 S 2 : C 45.98; H 3.51; N 4.87.
Found: C 45.78; H 3.62; N 4.67.
The compounds of Table 1 were prepared according to the general procedure described above in method 1 and Example 1.
TABLE 1______________________________________ ##STR11## MassExample Melting Analysis.sup.+ % SpectrumNumber R.sub.1 Point °C. C,H,N yield m/e (M.sup.+)______________________________________2 H 78-79 x,x,x 49 2703 3-F 75.5-77 x,x,x 49 2884 4-SCH.sub.3 141-141.5 x,x,x 67 3165 4-SO.sub.2 CH.sub.3 140-141 x,x,x 34 3486 3-Cl,4-F gum x,x,x* 52 339.sup.@7 4-OCH.sub.3 75.4-75.7 x,x,x 41 3008 3-Cl 84-86.5 x,x,x 66 3049 2,3-diCH.sub.3 140-141.4 x,x,x 47 29810 3-CF.sub.3 59-60 x,x,x 60 33811 3-CH.sub.3,4-F 100-101 x,x,x 42 30212 4-Cl 98-99.5 x,x,x 32 30413 2,4-diCl 83.5-84.5 x,x,x 12 33814 2,4-diF 75 x,x,x 71 30615 3-CH.sub.3 88-90 x,x,x 55 28416 2-CH.sub.3,4-F 86-86.5 x,x,x 64 30217 2-Br,4-F 99.6-101.9 x,x,x 62 36718 3,5-diCF.sub.3 114-116 x,x,x 71 40619 2-Cl,5-CF.sub.3 gum x,x,x 52 37220 3-i-Pr gum x,x,x 312______________________________________
Substitution of 1-naphthol, 2-naphthol or 5,6,7,8-tetrahydro-1-naphthol for the phenol in the general procedure described above gives the compounds of Table 1 B.
TABLE 1B______________________________________ ##STR12## MassExample Melting Analysis.sup.+ SpectrumNumber Aryl Ring Point °C. C,H,N m/e (M.sup.+)______________________________________21 1-Naphthyl 102-105.5 x,x,x 32022 2-Naphthyl 122-122.5 x,x,x 32023 5,6,7,8-Tetrahydro- 112-116 x,x,x 324 1-naphthyl______________________________________
Method 2: General Procedure for the Synthesis of Compounds R ##STR13##
The appropriate 2-acetamido-5-phenoxy thiophene (1 equivalent), synthesized as described above, is dissolved in THF (7.5 mL per mmol) and cooled to -78° C. Lithium diisopropylamide (1.1 equivalents) is added and the solution stirred for an additional ten minutes before the appropriate alkyl or aryl sulfonyl chloride (1.1 equivalents) is added. After 1-2 hours the mix is evaporated in vacuo and redissolved in ethanol. Concentrated ammonium hydroxide (0.5 mL per mmol) is added and after 30-60 minutes the mixture is again evaporated in vacuo. The residue is partitioned between methylene chloride and 1N HCI. The organic layer is washed with water, dried over magnesium sulfate and concentrated in vacuo. The resulting 2-alkyl or arylsulfonamido-5-phenoxy thiophene is purified via silica gel column chromatography eluted with hexane-ethyl acetate.
The compounds of Table 2 were prepared according to the general procedure described above in Method 2.
TABLE 2______________________________________ ##STR14## MassExample Melting Analysis.sup.+ % SpectrumNumber R.sub.2 Point °C. C,H,N yield m/e (M.sup.+)______________________________________24 n-Butyl gum x,x,x 64 31225 i-Propyl 185-194 x,x,x 7 29826 n-Octyl 35-40.5 x,x,x 64 36827 Phenyl 96-110.5 x,x,x 9 332______________________________________
Method 3: General Procedure for the Synthesis of Compounds H ##STR15##
2-Nitro-5-bromothiophene (1 equivalent) is dissolved in dimethylformamide (3 mL per mmol) and to the resulting solution is added the appropriately substituted aryl or alkyl thiol (1 equivalent) and potassium carbonate (2 equivalents). This mixture is stirred at 70° C. for 4-8 hours and then poured into water and the crude solid filtered and washed with water to give the intermediate 2-Nitro-5-arylthio- or 2-Nitro-5 -alkylthio-thiophene.
The above substituted thiophene is converted to the corresponding thiophenoxy and thioalkoxy derivatives as described above for the above 2-methane-suffonamido-5-phenoxy thiophenes.
The compounds of Table 3 were prepared according to the general procedure described above in Method 3.
TABLE 3______________________________________ ##STR16## MassExample Melting Analysis.sup.+ SpectrumNumber R Point °C. C,H,N m/e (M.sup.+)______________________________________28 Phenyl 115-118 x,x,x 28629 cyclohexyl 63-64 x,x,x 29230 n-Pentyl oil x,x,x 280______________________________________
Method 4: General Procedure for the Synthesis of Compounds M ##STR17##
5Nitrothiophene-2-carboxaldehyde (1 equivalent) is dissolved in anhydrous tetrahydrofuran (2.5 mL per mmol), after cooling to -78° C., the appropriate arylmagnesium bromide (1.1 equivalents) is added and the resulting mixture stirred for 30 minutes before quenching with aqueous ammonium chloride. The product is extracted with ethyl acetate and the organic layer washed with water, dried over magnesium sulfate and concentrated to give the 5-Nitrothiophene-2-phenylmethylcarbinol which is purified via silica gel chromatography.
To the above 5-Nitrothiophene-2-phenylmethylcarbinol (1 equivalent) in methylene chloride (2 mL per mmol) is added triethylsilane (3 equivalents). The reaction mix is cooled to 0° C. and borontrifluoride etherate (3 equivalents) is added and the reaction stirred for 16 hours, saturated aqueous sodium carbonate is added and the product extracted with ether. The organic layer is washed with water, dried over magnesium sulfate and evaporated in vacuo to give the 5-benzyl-2-nitro-thiophene derivative.
The above substituted 5-benzyl-2-nitro-thiophene (1 equivalent) is dissolved in acetic acid (3 mL per mmol) and treated with acetic anhydride (1 equivalent) and iron powder (4 equivalents). The resulting mixture is heated at 80° C. for 4-8 hours and then poured into water and the crude solid filtered and purified via chromatography on silica gel to yield the desired 2-acetamido-5-benzyl-thiophenes.
The 2-acetamido-5-benzyl thiophene (1 equivalent) is dissolved in THF (7.5 mL per mmol) and cooled to -78° C. Lithium diisopropylamide (1.1 equivalents) is added and the solution stirred for an additional ten minutes before methanesulfonyl chloride (1.1 equivalents) is added. After 1-2 hours the mix is evaporated in vacuo and redissolved in ethanol. Concentrated ammonium hydroxide (0.5 mL per mmol) is added and after 30-60 minutes the mixture is again evaporated in vacua. The residue is partitioned between methylene chloride and 1 N HCI. The organic layer is washed with water, dried over magnesium sulfate and concentrated in vacuo. The resulting 2-methane-sulfonamido-5-benzyl thiophene is purified via silica gel column chromatography eluted with hexane-ethyl acetate.
Example 31
A specific procedure for the synthesis of
N-(5-Benzylthien-2-yl)methanesulfonamide (31) ##STR18##
5-Nitrothiophene-2-carboxaldehyde (3.11 g, 20.0 mmol) was dissolved in anhydrous tetrahydrofuran (50 mL). After cooling to -78° C. phenylmagnesium bromide (22 mis of 1N sol'n in THF) was added and stirred for 30 minutes before quenching with aqueous ammonium chloride. The product was extracted with ethyl acetate and the organic layer was washed with water, dried over magnesium sulfate and concentrated to an oil which was purified on a silica gel column eluted with hexane-ethyl acetate 4:1 yielding 3.72 grams of 5-Nitro-thiophene-2-phenylmethylcarbinol (79%) as a dark brown oil.
To the above alcohol (1.05 g, 4.46 mmol) in methylene chloride (10 mL) was added triethylsilane (2.20 mL, 13.5 mmol). The reaction mix was cooled to 0° C. and boron trifluoride etherate (1.66 mL, 13.5 mmol) was added and the reaction was stirred for 16 hours after which time 50 mL of saturated aqueous sodium carbonate was added. The product was extracted with ether, the ether layer was washed with water, dried over magnesium sulfate and evaporated in vacuo to give 2-benzyl-5-nitrothiophene as a brown oil (0.78 grams, 79%).
To 2-benzyl-5-nitrothiophene (1.88 g, 8.57 mmol) dissolved in 50 mL of a 1:1 mix of acetic acid-acetic anhydride was added iron powder (1.92 g, 34.4 mmol). The resulting mixture was vigorously stirred with a mechanical stirrer at 80° C. for 5 hours before being poured into ice water. The crude solid was filtered, washed with water and purified on a silica gel column eluted with hexane-ethyl acetate 5:2 giving N-(5-Benzylthien-2-yl)acetamide 0.930 g (47% !. Mp 141-142° C.
The above acetamide (0.82 g, 3.5 mmol) was dissolved in anhydrous THF (25 mL). This solution was cooled to -78° C., lithium diisopropylamide (2.33 mL of 1.5N sol'n) added and after 10 minutes methanesulfonyl chloride (0.27 mL, 3.5 mmol) was added and the mix was stirred at room temperature for one hour before being evaporated in vacuo. The residue was resolved in 50 mL of methanol and 5 mL of concentrated ammonium hydroxide was added, stirred for one hour and evaporated in vacuo. The product was partitioned between methylene chloride and 1N HCI. The organic layer was washed with water, dried over sodium sulfate, concentrated in vacuo and purified on a silica gel column eluted with hexane-ethyl acetate 3:1 giving the title compound 0.51 g (55%)! as a yellow solid. Mp 91°-92° C., CIMS (m/e) 268 (MH + ).
Method 5: General Procedure for the Synthesis of Compounds Q ##STR19##
2-Bromo-5-nitrothiophene (1 equivalent) is dissolved in toluene (3 mL per mmol) and to this solution is added the appropriate aryl boronic acid (1.08 equivalents), tetrakis(triphenylphosphine)palladium (0) (3 mole%), potassium carbonate (2 equivalents) and water (1.5 mL per mmol). The resulting mixture is refluxed for 18 hours after which time the layers are separated, the organic layer is evaporated to a crude solid which is recrystallized from ethanol-water to give the desired 2-nitro-5-aryl-thiophene.
The above 2-nitro-5-aryl-thiophenes are converted to the corresponding N-5-aryl-thien-2-yl!methanesulfonamides by the methods previously described above.
Example 32
A specific procedure for the synthesis of:
N-5- (4-fluoro)phenyl-thien-2-yl!methanesulfonamide (32) ##STR20##
2-Bromo-5-nitrothiophene (3.50 g, 16.8 mmol) was dissolved in toluene (50 mL). To this solution was added 4-fluorophenyl boronic acid (2.52 g, 18.0 mmol), tetrakis(triphenylphosphine)paJladium (0) (0.58 g, 3 mole%), potassium carbonate (4.56 g, 33.0 mmol) and water (25 mL) and the resulting mixture refluxed for 18 hours after which time the layers were separated. The organic layer was evaporated to a crude solid which was recrystallized from ethanol-water to give 2-nitro-5-(4-fluoro)phenylthiophene (2.99 grams (80%)1. Mp 129°-130° C.
The above biaryl compound (2.89 g, 12.9 mmol) was dissolved in a 1:1 mixture of acetic acid-acetic anhydride (50 mL). To this was added iron powder (2.89 g, 51.7 mmol) and the resulting mixture stirred at 80° C. for 5 hours after which time the mix was poured into ice-water and the crude solid filtered and washed with water. Recrystallization from ethanol-water yields N-5- (4-fluoro)phenyl-thien-2-yl!acetamide 2.60 grams (86%)!. Mp 141°-142° C.
The above acetamide (2.52 g, 11.0 mmol) was dissolved in anhydrous tetrahydrofuran (50 mL) and cooled to -78° C. To this was added lithium diisopropylamide (7.33 mL of 1.5M sol'n) and methanesulfonyl chloride (0.85 mL, 11.0 mmol). The mix was stirred for 30 minutes before it was evaporated in vacuo and redissolved in methanol (50 mL). Concentrated ammonium hydroxide (5 mL) was added and this was stirred for 30 minutes after which time the mix was again evaporated in vacuo and the product extracted with ethyl acetate. The organic layer was washed with 1N HCI then water and concentrated in vacuo. Purification on a silica gel column eluted with hexane-ethyl acetate 3:1 gave the title compound 0.69 g (23%)!. Mp 185.5°-187° C., CIMS (m/e) 272 (MH + ).
Substitution of phenyl boronic acid for 4-fluorophenyl boronic acid in the above procedure yields N-5- phenyl-thien-2-yl!methanesulfonamide (33) as a white solid, Mp 180°-181° C., CIMS (m/e) 254 (MH + ).
Method 5: General Procedure for the Synthesis of Compounds V ##STR21##
2-Nitro-3-bromothiophene Ann. Chem., 512,136 (1934)!(1 equivalent) is dissolved in dimethylformamide (5 mL per mmol) and to the resulting solution is added the appropriately substituted phenol (1 equivalent) and potassium carbonate (2 equivalents). This mixture is stirred for 4-8 hours at 80° C. and then poured into water and the solid filtered, washed with water and dried in vacuao to give the intermediate 2-nitro-3-phenoxythiophene.
The above substituted 2-nitro-3-phenoxythiophene (1 equivalent) is suspended in concentrated HCI (4 mL per mmol), Tin powder (3 equivalents) is added and the mixture stirred at 50°-70° C. for 4-6 hours after which time the resulting solid is filtered, washed with ether and dried in vacuo to give the tin double salt. The tin salt is dissolved in pyridine (10 mL per mmol) and cooled to 0° C. Methanesulfonyl chloride (1 equivalent) is added, stirred for 16-20 hours and poured into water. The product is extracted with ethyl acetate, the organic layer washed with 1N HCI, then water and dried over magnesium sulfate. The resulting 2-methanesulfonamido-3-phenoxy thiophene is purified via silica gel column chromatography eluted with hexane-ethyl acetate.
The compounds of Table 4 were prepared according to the general cedure described above in Method 5.
TABLE 4______________________________________ ##STR22## MassExample Melting Analysis.sup.+ SpectrumNumber R Point °C. C,H,N m/e (M.sup.+)______________________________________34 4-F gum x,x,x 28835 H 98-101.5 x,x,x 27036 2,4-diF gum x,x,x 30637 3-Ph gum x,x,x 34638 2,4-diCH.sub.3 82-89 x,x,x 29839 4-CF.sub.3 100-104 x,x,x 33840 3-F gum x,x,x 28841 2-Ph 107-111 x,x,x 34642 4-F,2-CH.sub.3 gu;m x,x,x 30243 3,4-diOCH.sub.3 135-137 x,x,x 33044 1-Naphthyl 37-45 x,x,x 32045 2-Naphthyl gum x,x,x 320______________________________________
Biological Results
Procedure I
RBL-1 cell 5-lipoxygenase and cyclooxugenase - Homogenate
Rat basophilic leukemia cells (RBL-1; 5×10 7 viable cells/mL) were disrupted by homogenization on ice (four 20 sec bursts) with a Brinkman polytron. Complete cell breakage was verified microscopically. The homogenate was then centrifuged at 9,220×g for 48 minutes at 4° C. The pellet was discarded and the supernatant was saved as the source of enzymes. The supernatant was pre-incubated for five minutes at 37° C. in the presence of 2 mM of CaCl2 and compound or vehicle (1% DMSO). The conversion of AA into products by CO and LO was initiated by adding 10 μL (50 μCi) of 1- 14 C-AA to each tube and incubated at 37° C. for 20 minutes. The reaction was stopped by adjusting the pH of each sample to 3 to 3.5 with 2M formic acid. Samples were extracted with three volumes of chloroform to isolate the products of 5-LO formed during the reaction. Fractions were dried under nitrogen, then resuspended in 40 μL of chloroform and spotted onto silica gel HL plates. The plates were developed in A-9 solvent. The dried plates were analyzed using a Bioscan Imaging TLC scanner to determine the percentage of radiolabelled M converted to 5-HETE (LO product) and PGD 2 (CO product) in each sample.
Procedure II
RBL-1 Cell 5-Lipoxygenase and cyclooxygenase - Whole cells
The ability to inhibit 5-LO and CO in intact RBL-1 cells was also evaluated. RBL-1 cells were maintained in culture in minimal essential medium (Bio*Whittaker, Walkersville, Md.), containing 12.5% fetal calf serum, 10 mg/mL streptomycin, 10 l.U./mL penicillin G, 50 mg/mL gentamycin and 2 mM L-glutamine (Bio*Whittaker, Walkersville, Md.). Cells were collected by centrifugation, washed once in HBSS, and resuspended at a concentration of 1×10 5 cells/mL. Cells were incubated in the presence of vehicle or drug then centrifuged at 800×g for 10 minutes at 4° C. The supernatant was removed by aspiration and the cells were resuspended in 0.5 mL of HBSS. The reaction was started by the addition of 20 μg/mL of calcium ionophore A 23187 (mixed calcium and magnesium salts, Calbiochem, La Jolla Calif.) and allowed to proceed for 15 minutes, then stopped by plunging the tubes into a slush ice bath. The conversion of M to 5-LO products was initiated by the addition of 10 μL (50 uCi) of 1- 14 C-AA. Products were isolated by acidification and extraction, followed by thin layer chromatography analysis as described above. Radioactive areas corresponding to authentic 5-LO (5-HETE) and CO (PGD2) products were quantitated by the Bioscan 2000 Imaging System.
Procedure III
Human Prostaglandin H 2 Synthase Typ II (Cox-2) Whole Cell Assay (Multiple Concentrations)
ECV-304 (human, endothelial, umbilical cord) cells are maintained in culture in a suitable medium, and are trypsinized and plated at a density of 1×106 cells per well of a 6 well plate prior to assay. Approximately 28 hours later, 50 μg/ml PMA and 1 mM ionomycin (both final concentrations) are added to each well and incubated for an additional 16 hours. Vehicle or test compounds are incubated with the cells for five minutes prior to initiation of Cox-2 enzyme activity by the addition of 30 μM arachidonic acid. Ten minutes later, an aliquot of the supernatant is withdrawn and the amount of PGE 2 present quantitated by radioimmunoassay. Activity, reported as percent inhibition of PGE 2 produced, is calculated as follows:
______________________________________ Procedure III (COX-2) Wh Cell Procedure II Procedure IExample 1% @ 10 μM (5-LO) Wh Cell (5-LO) Homog.# IC.sub.50 (μM) IC.sub.50 (μM) IC.sub.50 (μM)______________________________________ 2 4.22 0.47 0.0712 18 0.66 0.07513 5.8 0.65 0.0915 1.69 0.31 0.12 3 13% 0.49 0.1614 1.97 0.73 0.15 4 39% 0.66 0.10 1 1.81 0.46 0.1311 1.18 0.31 0.0221 3.0 0.80 0.07 6 5.3 0.89 0.03 7 0% 1.45 0.0228 33% 0.7 0.19 8 10.3 0.5 0.06 9 54% 0.66 0.0633 31% 0.79 0.1122 10 0.77 0.0624 10 1.12 0.3625 16% 1.04 0.0527 44% 0.9 0.1026 8% 2.9 0.30 5 0% 38.5 1.810 1.02 0.78 0.0616 1.90 1.09 0.0923 10 0.5 0.0520 36% 4.7 0.6131 45% 0.38 0.1129 9.10 2.39 0.0717 5.29 1.4 0.0630 2.76 0.63 0.0418 8% 6.5 0.3119 29% 1.8 0.1432 3% 2.1 0.15______________________________________ ##STR23##
The compounds of Table 4 (34-45) were evaluated in Procedures I-III. The compounds were found to be inhibitors of Cox-2 activity (Procedure I) but were ineffective as inhibitors of 5-LO (Procedures II and III) in either cell free or whole cell assays.
Procedure IV
Carrageenan-Induced Localized Inflammation In Subcutaneous Chambers Implanted In Beagle Dogs
Sterile perforated teflon chambers (wiffle golf balls) were surgically implanted subcutaneously in the dorsal neck fold of beagle dogs (8-13 kg, mixed sex). After a recovery period of 1 month, a 1 ml sample of fluid exudate from each dog was aspirated from within the chamber using a 1 ml syringe and 20 gauge 1 inch needle inserted through one of the perforations in the ball. Immediately after obtaining the sample, 1.5 ml of 0.33% sterile carrageenan lambda (Sigma Chemical Co., St. Louis, Mo.) was injected into the chamber. Dilutions of the baseline samples were made in saline and analyzed for leukocyte count using a Coulter Counter (6.08-50 μm range). The sample was also analyzed for concentrations of PGE2 and LTB4 by adding 200 μl of sample to 1 ml ethanol and centrifuging the precipitate (1,500 X g, 7 min). The supernatant was aspirated and stored at 0° C. until enzyme linked immunosorbant assays (ELISAs) were performed (ELISA Technologies, Lexington, Ky.). Samples were also drawn at 5 and 24 hours post carrageenan challenge and treated in a similar manner. Local inflammation is characterized by elevated levels of eicosanoids (PGE 2 and LTB 4 ) and by an influx of leukocytes into the chamber. Elevated levels of PGE 2 in the fluid exudate is indicative of an inducable cyclooxygenase-2 (COX-2) mediated response.
Blood samples were drawn simultaneously with the fluid exudates for evaluation of non-inflammatory production of eicosanoids. Samples were collected with 4.5 ml lithium-heparin monovettes (Sarstedt) and Vacutainer blood collection sets (21 G 3/4inch). One ml of each blood sample was treated with 50 μl calcium ionophore A23187 (0.28 mg/ml suspended in 4% DMSO/HBSS), followed by a 15 minute incubation at 37° C. The reaction was stopped by placing the samples in an ice slush bath for 5 minutes. The samples were then centrifuged (1,500 X g, 7 minutes), and 100 μl plasma were added to 1 ml cold methanol to extract the eicosanoids. The extracted samples were centrifuged (1,500 X g, 7 minutes) and the supernatant stored at 0° C. until ELISAs were performed to evaluate eicosanoid (PGE 2 and LTB 4 ) production. Since the PGE 2 produced in peripheral blood is derived mainly from the platelets, it is indicative of the constitutive COX-1 response.
Drug effects can be evaluated on several important aspects of inflammation using this in-vivo assay. Inhibition of leukocyte influx by administration of a therapeutic agent at the time of carrageenan challenge represents anti-inflammatory activity. PGE 2 and/or LTB 4 inhibition may give some insight into the mechanism of action of the agent. Selectivity of a COX inhibitor can be determined by comparing PGE 2 inhibition in peripheral blood (COX-1) to that of the inflammatory fluid exudate in the chamber (COX-2).
The dog inflammation model described in Procedure IV allows for the simultaneous evaluation of eicosanoid production in the periphery and at a site of inflammation. FIG. 1 graphically depicts the effects of compound 1 on ex vivo LTB 4 production in dogs five hours following oral administration of compound. The results indicate that compound 1 inhibited peripheral LTB4 production (IC 50 =4.4 mg/kg) five hours after oral administration of compound. No inhibition of LTB 4 production in whole blood was detected at 24 hours following dosing. When the exudate in the inflammatory chambers was examined, compound 1 caused a dose related inhibition of both the accumulation of inflammatory cells in the exudate and LTB 4 levels measured in the fluid . The ED 50 for inhibition of both cellular influx and fluid LTB 4 levels was <0.01 mg/kg. These data indicate that compound 1 is an orally active and potent inhibitor of an inflammatory event (cell infiltration) which is thought to be mediated by products (LTB 4 ) of 5-LO.
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2,5-Disubstituted thiophene derivatives, and more particularly, to 2-aryloxy-5-alkansulfonamido-thiophenes of the general formula: ##STR1## Wherein, R 2 is CF 3 , C 1 -C 10 alkyl, or phenyl;
X is O, S, or CH 2 ; and
R is aryl, C 1 -C 10 alkyl, or C 3 -C 8 cycloalkyl; which compounds are pharmacologically active in alleviating inflammation, asthma, arthritis, hypersensitivity, myocardial ischemia and dermatological conditions, such as, psoriasis and dermatitis, and gastrointestinal inflammatory conditions, such as, inflammatory bowel syndrome.
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[0001] The present invention relates to a production method for a semi-finished product, especially an elongated semi-finished product having at least two differently profiled sections, for instance, an anchor bolt.
BACKGROUND
[0002] A thread on an anchor bolt can be created by means of cross-rolling. A cylindrical blank is inserted between two roller profiles and is then rolled along the roller profiles while being rotated around its axis. In this process, the roller profiles emboss ridges for the thread into the circumference of the blank. The high quality of the thread that can be achieved is due, among other things, to the rolling procedure and to the associated uniform radial dimensions.
SUMMARY OF THE INVENTION
[0003] A drawback is that the length of the thread is prescribed by the width of the roller profiles employed.
[0004] The present invention provides a method for creating a thread in an elongated semi-finished product comprises the following steps: shaping, especially lengthwise rolling, of at least two lengthwise grooves into a blank and lengthwise rolling of a thread into the areas circumferentially delimited by the grooves. The distance from the beds of the grooves to the axis of the blank is smaller than the distance from the root of the thread to the axis. The distance from the root of the thread to the axis equals half the core diameter of the thread.
[0005] Lengthwise rolling is actually unfavorable for creating a thread since, in contrast to cross-rolling, it does not take into account the rotating symmetry of the thread. The material that flows during the rolling procedure is not pushed uniformly along the circumference. The material can escape in an uncontrolled manner in the area of the lateral edges of the roller profiles. The grooves can collect the laterally escaping material in order to prevent the formation of burrs or other structures protruding radially into the thread. Here, weakening of the thread due to gaps formed in the thread by the grooves has to be accepted.
[0006] One embodiment provides that the blank is conveyed along a direction of movement. Rollers that serve to shape the thread rotate around a rotational axis perpendicular to the direction of movement.
[0007] One embodiment provides that, in the case of a number N of grooves, the rollers are rotated with respect to the grooves around the axis by a quotient of 180° relative to the number N. A lateral edge of a roller profile of one of the rollers can be moved in a plane with the axis and with one of the grooves. The grooves can likewise be rolled lengthwise. The rollers for the lengthwise rolling of the grooves are arranged so as to be rotated around the axis by the quotient with respect to the rollers for the thread rolling. The rollers for the thread rolling can surround the blank annularly.
[0008] A semi-finished product according to the invention, especially an anchor bolt, has a cylindrical section into whose circumference at least two grooves have been formed that run parallel to the axis of the cylindrical section. The areas between the grooves are shaped to form segments of a thread. One embodiment proves that flanks of the thread each adjoin two of the grooves. The percentage of the thread on the circumference of the semi-finished product can amount to at least 80%. One embodiment provides that each groove extends over the entire length of the thread.
[0009] One embodiment provides that another section is shaped to form a conical expansion element.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The description below explains the invention on the basis of embodiments and figures provided by way of an example. The figures show the following:
[0011] FIG. 1 : an anchor;
[0012] FIG. 2 : a cross section in the plane II-II through the anchor;
[0013] FIGS. 3 and 4 : a method step for the production of the anchor;
[0014] FIGS. 5 and 6 : another method step for the production of the anchor.
[0015] Unless otherwise indicated, identical elements or elements having the same function are designated with the same reference numerals in the figures.
DETAILED DESCRIPTION
[0016] FIG. 1 shows an anchor 10 that, by way of example, is configured as an expansion anchor with an anchor bolt 11 and an expansion sleeve 12 . Along the axis 13 of the anchor bolt 11 , there is an expansion element 14 , a neck 15 , a shank 16 , and a thread 17 . The expansion sleeve 12 , which can move along the anchor bolt 11 , is pre-mounted on the neck 15 . The outer diameter 18 of the expansion sleeve 12 is about the same size as the largest diameter 19 of the expansion element 14 . The anchor 10 is driven into a drilled hole having a diameter corresponding to the outer diameter 18 of the expansion sleeve 12 . A ring-shaped collar 20 between the neck 15 and the thread 17 can prevent the expansion sleeve 12 from sliding off of the anchor bolt 11 . When the anchor 10 is tightened against the substrate, for example, by means of a nut 21 , the expansion element 14 is pulled into the expansion sleeve 12 and the expansion sleeve 12 is firmly clamped onto a side wall of the drilled hole.
[0017] The thread 17 is interrupted by several grooves 30 that run parallel to the axis 13 . The grooves 30 are preferably uniformly distributed around the axis 13 , for instance, four grooves at intervals of 90°. The grooves 30 preferably extend along the entire length of the thread 17 . Therefore, the single-flight thread 17 is made up of several segments 31 . Each of the segments 31 has the characteristic properties of a thread 17 such as, for instance, a rated diameter 32 , a core diameter 33 , a pitch angle 34 , a flank angle 35 and a thread lead 36 . The segments 31 are preferably configured in the form of a V-thread and they form the flanks of the thread. Preferably, the characteristic properties of all segments 31 are identical. The flank angle amounts to, for instance, 60°. The pitch angle 34 is preferably between 2° and 5°. The segments 31 only surround a fraction of the circumference; in case of the, for example, four grooves 30 , between 75° and 85°.
[0018] The groove bed 37 of the groove 30 is preferably at a constant distance 38 from the axis 13 . Half of the core diameter 33 of the thread 17 is preferably greater than the distance 38 , that is to say, the thread root 39 is located further away from the axis 13 than the grooves 37 are. The grooves 30 are shaped into the anchor bolt 11 at a greater depth than the thread 17 .
[0019] The width of the grooves 30 in the circumferential direction 41 is considerably smaller than the width 40 of the segments 31 . Preferably, the segments 31 take up a portion of more than 80% (approximately)300° of the total circumference. The boundaries of the segments 31 can be defined, for instance, as the points where the trailing flank 42 is only at a distance from the thread root 39 over half of its maximum distance (equal to one-fourth of the difference between the rated diameter 32 and the core diameter 33 ).
[0020] By way of an example, FIGS. 4 to 6 illustrate a production method for the anchor bolt 11 . FIGS. 4 and 6 depict the cross sections through the anchor bolt 11 and a production tool in the planes IV-IV and VI-VI, respectively. A blank 50 is, for instance, a cylindrical piece of wire. The unshaped cross section of the wire is preferably circular. The diameter 51 of the wire is constant and harmonized with the thread 17 , at least in a section 52 for the thread 17 . For example, the diameter 51 of the wire can be the same as the flank diameter of the thread 17 , that is to say, approximately the mean value of the outer and core diameter of the thread 17 . The blank 50 provided by way of an example has already been shaped to form the expansion element 14 and the neck 15 in a section 53 by means of the rolling procedure. As an alternative, the entire blank 50 can have one diameter, especially if the thread 17 is supposed to be created along the entire blank 50 .
[0021] The blank 50 is fed to a first roller stand 54 that rolls the grooves 30 into the section 52 . The first roller stand 54 has several rollers 55 between which the blank 50 passes. The rollers 55 are rotated around their axes 56 , which are oriented perpendicular to the direction of movement 57 of the blank 50 . Each one of the rollers 55 embosses a groove 30 into the blank 50 along the axis 13 . The roller stand 54 shown has four rollers 55 that grip the entire circumference of the blank 50 . An alternative embodiment has two or more pairs of opposite rollers and the orientation of adjacent pairs with respect to the axis 13 differs.
[0022] The blank 50 provided with the grooves 30 is conveyed to a second roller stand 58 that creates the thread 17 . The second roller stand 58 has several rollers 59 between which the blank 50 passes. The rollers 59 are rotated around their axes 60 , which are oriented perpendicular to the direction of movement 57 of the blank 50 . Each of the rollers 59 embosses segments 31 of the thread into the blank 50 along the axis 13 . The advantageously configured roller stand 58 surrounds the circumference of the blank 50 . The number of rollers 59 corresponds to the number of previously embossed grooves 30 . Each of the rollers 59 completely covers an angular section 61 located between two grooves 30 . Each lateral edge 62 of the roller profiles is in a plane with one of the grooves 30 . The roller profile preferably does not touch the groove bed 37 . The groove bed 37 can be partially filled by flowing material during the rolling procedure.
[0023] The rollers 59 of the second roller stand 58 are arranged so as to be rotated around the axis 13 by 45° with respect to the rollers 55 of the first roller stand 54 . The angle of rotation corresponds to the quotient of 180° and the number of grooves 30 .
[0024] The blank 50 can be fed through the rollers in one direction of movement. As an alternative, the blank 50 can be preferably pushed between the rollers and then removed from the rollers opposite to the direction of movement.
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The production method according to the invention for creating a thread in an elongated semi-finished product comprises the following steps: shaping, especially lengthwise rolling, of at least two lengthwise grooves into a blank and lengthwise rolling of a thread into the areas circumferentially delimited by the grooves. The distance from the beds of the grooves to the axis of the blank is smaller than the distance from the root of the thread to the axis.
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This application claims benefit of U.S. Provisional application No. 60/108,786 filed Nov. 17, 1998.
FIELD OF THE INVENTION
This invention relates to a novel, highly efficient and general process for making 2-(2-oxyaryl)-4,6-bisaryl-1,3,5-triazines class of trisaryl-1,3,5-triazine UV absorbers and their precursors, 2-halo-4,6-bisaryl-1,3,5-triazines, from cyanuric halide. More specifically, the invention relates to a novel process for the synthesis of triazine compounds in the presence of a reaction facilitator comprising at least one Lewis acid and at least one reaction promoter. The process includes the reaction of a cyanuric halide with substituted or unsubstituted aromatic compounds to produce 2-halo-4,6-bisaryl-1,3,5-triazine compounds. This process produces halo-bisaryl-1,3,5-triazine compounds in higher yields than are possible using present methods. The triazine compounds that are produced are precursors of triazine UV absorbers which are used to stabilize organic materials against damage by light, heat, oxygen, or other environmental forces. The process of producing such UV absorbers can be carried out step-wise or continuously in an one-pot reaction process.
BACKGROUND OF THE INVENTION
Triazine UV absorbers are an important class of organic compounds which have a wide variety of applications. One of the most important areas of applications is to protect and stabilize organic materials such as plastics, polymers, coating materials, and photographic recording material against damage by light, heat, oxygen, or environmental forces. Other areas of applications include cosmetics, fibers, dyes, etc.
Triazine derived UV absorbers are a class of compounds that typically include at least one 2-oxyaryl substituent on the 1,3,5-triazine ring. Triazine based UV absorber compounds having aromatic substituents at the 2-, 4-, and 6-positions of the 1,3,5-triazine ring and having at least one of the aromatic rings substituted at the ortho position with a hydroxyl group or blocked hydroxyl group are generally preferred compounds.
In general this class of triazine UV absorber compounds is well known in the art. Disclosures of a number of such trisaryl-1,3,5-triazines can be found in the following U.S. patents, all of which are incorporated by reference as fully set forth herein: U.S. Pat. Nos. 3,118,887; 3,242,175; 3,244,708; 3,249,608; 3,268,474; 3,423,360; 3,444,164; 3,843,371; 4,619,956; 4,740,542; 4,775,707; 4,826,978; 4,831,068; 4,962,142; 5,030,731; 5,059,647; 5,071,981; 5,084,570; 5,106,891; 5,185,445; 5,189,084; 5,198,498; 5,288,778; 5,298,067; 5,300,414; 5,323,868; 5,354,794; 5,364,749; 5,369,140; 5,410,048; 5,412,008; 5,420,008; 5,420,204; 5,461,151; 5,476,937; 5,478,935; 5,489,503; 5,543,518; 5,538,840; 5,545,836; 5,563,224; 5,575,958; 5,591,850; 5,597,854; 5,612,084; 5,637,706; 5,648,488; 5,672,704; 5,675,004; 5,681,955; 5,686,233; 5,705,643; 5,726,309; 5,726,310; 5,741,905; and 5,760,111.
A preferred class of trisaryltriazine UV absorbers (UVAS) are based on 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazines, i.e., compounds with two non-phenolic aromatic groups and one phenolic aromatic group advantageously derived from resorcinol. The 4-hydroxyl group of the parent compounds, 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazines, are generally functionalized to make 2-(2-hydroxy-4-alkoxyaryl)-4,6-bisaryl-1,3,5-triazine compounds for end use.
A number of commercial products exist in which the para-hydroxyl group of the phenolic ring is functionalized and the non-plienolic aromatic rings are either unsubstituted phenyl (e.g., Tinuvin® 1577) or m-xylyl (e.g. Cyasorb® UV-1164, Cyasorb® UV-1164L, Tinuvin® 400, and CGL-1545). These UV absorbers are preferred because they exhibit high inherent light stability and permanence compared to other classes of UV absorbers such as benzotriazole and benzophenone compounds.
There are several processes known in the literature for the preparation of triazine based UV absorbers. (See, H. Brunetti and C. E. Luethi, Helvetica Chimica Acta, 1972, 55, 1566-1595, S. Tanimoto et al., Senryo to Yakahin, 1995, 40(120), 325-339).
A majority of the approaches consist of three stages. The first stage, the synthesis of the key intermediate, 2-chloro-4,6-bisaryl-1,3,5-triazine, from commercially available materials can involve single or multi-step processes. Thereafter in the second stage, 2-chloro-4,6-bisaryl-1,3,5-triazine is subsequently arylated with 1,3-dihydroxybenzene (resorcinol) or a substituted 1,3-dihydroxybenzene in the presence of a Lewis acid to form the parent compound 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine. The parent compound 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine, as mentioned above, may be further functionalized, e.g., alkylated, to make a final product 2-(2-hydroxy-4-alkoxyaryl)-4,6-bisaryl-1,3,5-triazine.
There have been several approaches reported in the literature on the synthesis of the key intermediate 2-chloro-4,6-bisaryl-1,3,5-triazine. Many of these approaches utilize cyanuric chloride, a readily available and inexpensive starting material. For example, cyanuric chloride is allowed to react with aromatics (ArH, such as m-xylene) in the presence of aluminum chloride (Friedel-Crafts reaction) to form 2-chloro-4,6-bisaryl-1,3,5-triazine, which is allowed to react in a subsequent step with resorcinol to form 2-(2,4-dihydroxyphenyl)-4,6-bisaryl-1,3,5-triazine (See, U.S. Pat. No. 3,244,708). There are several limitations to this process, viz., the reaction of cyanuric chloride with aromatics is not selective and leads to a mixture of mono-, bis-, and tris-arylated products including unreacted cyanuric chloride (See, Scheme 1). The desired product, 2-chloro-4,6-bisaryl-1,3,5-triazine, must be isolated by crystallization or other purification methods before further reaction.
Another major drawback of the above mentioned process is that the reaction of cyanuric chloride with aromatics is not generally applicable to all aromatics. It is well known in the literature that the process provides a useful yield of the desired intermediate, 2-chloro-4,6-bisaryl-1,3,5-triazine, only when m-xylene is the aromatic reagent (GB 884802). With other aromatics, an inseparable mixture of mono-, bis-, and trisaryl products are formed with no selectivity for the desired 2-chloro-4,6-bisaryl-1,3,5-triazine (See, H. Brunetti and C. E. Luethi, Helvetica Chimica Acta, 1972, 55, 1575; and S. Tanimoto and M. Yamagata, Senryo to Takahin, 1995, 40(12), 325-339). U.S. Pat. No. 5,726,310 describes the synthesis of m-xylene based products. 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine is first synthesized and without isolation allowed to react with resorcinol in a one-pot, two-step process to produce 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, which is subsequently purified by crystallization. A one pot process for preparing asymmetric tris-aryl-1,3,5-triazines from cyanuric chloride as well as from mono-aryl-dichloro triazines was earlier described in U.S. Pat. No. 3,268,474.
Several approaches were developed in an attempt to solve the above mentioned problems related to the formation of the key intermediate 2-chloro-4,6-bisaryl-1,3,5-triazine from cyanuric chloride. For example, cyanuric chloride is allowed to react with an aryl magnesium halide (Grignard reagent), to prepare 2-chloro-4,6-bisaryl-1,3,5-triazine (See, Ostrogovich, Chemiker-Zeitung, 1912, 78, 738; Von R. Hirt, H. Nidecker and R. Berchtold, Helvetica Chimica Acta, 1950, 33, 365; U.S. Pat. No. 4,092,466). This intermediate after isolation can be subsequently reacted in the second step with resorcinol to make a 2-(2,4-dihydroxyphenyl)-4,6-bisaryl-1,3,5-triazine (See, Scheme 2). This approach does not selectively synthesize 2-chloro-4,6-bisaryl-1,3,5-triazine; the mono- and tris-arylated products are formed in significant amounts (See, H. Brunetti and C. E. Luethi, Helvetica Chimica Acta, 1972, 55, 1575). Modifications with better results have been reported (See, U.S. Pat. No. 5,438,138). Additionally, the modified process is not suitable for industrial scale production and is not economically attractive.
Alternate approaches were developed to solve the selectivity problem when synthesizing 2-chloro-4,6-bisaryl-1,3,5-triazine using either a Friedel-Crafts reaction or Grignard reagents, however, all solutions required additional synthetic steps. One approach, is outlined in Scheme 3. In the first step, cyanuric chloride is allowed to react with 1 equivalent of an aliphatic alcohol to make in high selectivity a monoalkoxy-bischlorotriazine. In the second step, monoalkoxy-bischlorotriazine was allowed to react with aromatics in the presence of aluminum chloride to prepare intermediates monoalkoxy/hydroxy-bisaryltriazines. These intermediates were then converted to 2-chloro-4,6-bisarayl-1,3,5-triazines in the third step by reaction with thionyl chloride or PCl 5 . In the fourth step, 2-chloro-4,6-bisaryl-1,3,5-triazines were allowed to react with resorcinol to synthesize 2-(2,4-dihydroxyphenyl)-4,6-bisaryl-1,3,5-triazines. In the above process, the desired product was formed with high selectivity. However, the two additional
steps required made the process less attractive economically as an industrial process.
A similar approach is outlined in Scheme 4 (See, U.S. Pat. Nos. 5,106,972 and 5,084,570). The main difference is that cyanuric chloride was first allowed to react with 1 equivalent of alkanethiol, instead of an alcohol. As with the process summarized in Scheme 3, additional steps were required, making the process neither efficient nor economically feasible.
Recent improvements are disclosed in European patent application 0,779,280 A1 and Japanese patent application 09-059263.
Other approaches do not utilize cyanuric chloride as a starting material. For example, the synthesis of 2-chloro-4,6-bisaryl-1,3,5-triazine as disclosed in EP 0497734 A1 and as outlined in Scheme 5. In this process benzamidine hydrochloride is first allow to react with a chlorofornate and the resulting product is then dimerized. The resulting 2-hydroxy-4,6-bisaryl-1,3,5-triazine is converted to 2-chloro-4,6-bisaryl-1,3,5-triazine by treatment with thionyl chloride, which is subsequently allowed to react with resorcinol to synthesize 2-(2,4-dihydroxyphenyl)-4,6-bisaryl-1,3,5-triazine, as shown in Scheme 5.
An alternate approach for the preparation of 2-chloro-4,6-bisaryl-1,3,5-triazines is based on the reaction of aryl nitriles with phosgene in the presence of HCl in a sealed tube (S. Yanagida, H. Hayama, M. Yokoe, and S. Komori, J. Org. Chem., 1969, 34, 4125. Another approach is the reaction of N,N-dimethylbenzamide with phosphoryl chloride complex which is then allowed to react with N-cyanobenzamidine to form 2-chloro-4,6-bisaryl-1,3,5-triazine (R. L. N. Harris, Synthesis, 1990, 841). Yet another approach involves the reaction of polychloroazalkenes, obtained from the high temperature of chlorination of amines, with amidines to form 2-chloro-4,6-bisaryl-1,3,5-triazines (H. G. Schmelzer, E. Degener and H. Holtschmidt, Angew. Chem. Internat. Ed., 1966, 5, 960; DE 1178437). None of these approaches are economically attractive, and thus are not commercially feasible.
Finally, there are at least three approaches which do not require the intermediacy of 2-chloro-4,6-bisaryl-1,3,5-triazine for the preparation of the parent compound, 2-(2,4-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine. These approaches utilize benzonitriles or benzamidines as starting materials (See U.S. Pat. Nos. 5,705,643 and 5,478,935; WO 96/28431). The benzamidines are condensed with 2,4-dihydroxybenzaldehyde followed by aromatization (Scheme 6) or condensed with phenyl/alkyl 2,4-dihydroxybenzoates (Scheme 7) or 2-aryl-1,3-benzoxazine-4-ones (Scheme 8) to form 2-(2,4,-dihydroxyaryl)-4,6-bisaryl-1,3,5-triazine. These approaches have the drawback that the starting materials are expensive and may require additional steps to prepare. Moreover, overall yields are not satisfactory and the processes are not economically attractive.
In summary, although direct Lewis acid catalyzed bisarylation of cyanuric chloride to form the desired 2-chloro-4,6-bisaryl-1,3,5-triazine intermediate is the most economically attractive approach, this process has found only limited use due to the following problems:
1. Poor selectivity: Almost total lack of selectivity for bisarylation (with the exception of m-xylene where some selectivity is observed). Mono- and tris-arylated triazines are the major by-products.
2. Poor reactivity: Typical reaction conditions require high temperatures, long reaction times, and variable temperatures during the course of reaction. Aromatics with electron-withdrawing groups (such as chlorobenzene) fail to react beyond mono-substitution even at elevated temperatures and long reaction times.
3. Safety hazards: Temperature and addition rate must be carefully monitored to avoid an uncontrollable exotherm which may result in safety hazards.
4. Poor process conditions: The reaction slurry is either thick and difficult to stir or solid thereby making stirring impossible. The process requires various reaction temperatures and addition of reactants in portions over several hours.
5. Isolation problem/poor isolated yield: Separation and purification of the desired product is difficult and isolated yields are generally poor and commercially unacceptable.
6. Not a general process: The reaction cannot be used with different aromatics other than m-xylene.
Thus, there remains a need for improved methods for synthesizing triazine UV absorbers.
SUMMARY OF THE INVENTION
It has been now surprisingly discovered after extensive research that 2-halo-4,6-bisaryl-1,3,5-triazine can be prepared with unprecedented selectivity, efficiency, mild conditions, and in high yield by the reaction of cyanuric halide with aromatics in the presence of a reaction facilitator comprising at least one Lewis acid and at least one reaction promoter. This reaction is also unprecedently general as a variety of aromatics can be used to produce a wide selection of 2-halo-4,6-bisaryl-1,3,5-triazines. The novel approach includes the use of the reaction promoter in combination with at least one Lewis acid under certain reaction conditions to promote the formation of 2-halo-4,6-bisaryl-1,3,5-triazine compounds from cyanuric halide. Preferably, the Lewis acids and reaction promoters are combined to form a reaction facilitator in the form of a complex.
The present invention specifically relates to a process for the synthesis of a triazine compound by reacting a cyanuric halide of Formula V:
with at least one substituted or unsubstituted aromatic compound such as a compound of Formula II:
wherein R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbon atoms including substituted or unsubstituted biphenylene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, and optionally with either of R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , or R 9 and R 10 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, with the reaction being conducted in the presence of at least one reaction facilitator comprising at least one Lewis acid and at least one reaction promoter, optionally in an inert solvent, for a sufficient time at a suitable temperature and pressure to produce a triazine compound of Formula III:
wherein X is a halogen and Ar 1 and Ar 2 are the same or different and each may be the radical of a compound of Formula II:
In a further embodiment, the triazine compound of Formula III is further reacted with a compound of Formula IV:
wherein R 1 , R 2 , R 3 , R 4 , and R 5 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbons atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthalene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, optionally with either of R 3 and R 4 , or R 4 and R 5 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, and Y is a direct bond, O, NR″, or SR″ wherein R″ is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, optionally in the presence of an additional Lewis acid, additional reaction promoter, or additional reaction facilitator, for a sufficient time at a suitable temperature and pressure, optionally in the presence of an inert solvent, to produce a compound of Formula I:
The reaction to form the compound of Formula III and the reaction to form the compound of Formula I can be carried out without isolating the compound of Formula III.
Another embodiment relates to a process for synthesizing a triazine compound of Formula I:
wherein Ar 1 and Ar 2 are the same or different, and each independently is a radical of a compound of Formula II:
wherein R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbon atoms including substituted or unsubstituted biphenylene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, and optionally with either of R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , or R 9 and R 10 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, which comprises:
simultaneously reacting in the presence of a reaction facilitator comprising at least one Lewis acid and at least one reaction promoter, sufficient amounts of a cyanuric halide of Formula V:
where each X is independently a halide such as fluorine, chlorine, bromine or iodine, with a compound of Formula IV:
wherein R 1 , R 2 , R 3 , R 4 , and R 5 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbons atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthalene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, optionally with either of R 3 and R 4 , or R 4 and R 5 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, and Y is a direct bond, O, NR″, or SR″ wherein R″ is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, and a compound of Formula II:
for a sufficient time, at a suitable temperature and pressure to form the compound of Formula I.
Another embodiment relates to a process for synthesizing a triazine compound of Formula I:
wherein Ar 1 and Ar 2 are the same or different, and each independently is a radical of a compound of Formula II:
wherein R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbon atoms including substituted or unsubstituted biphenylene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, and optionally with either of R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , or R 9 and R 10 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, which comprises:
reacting in the presence of a reaction facilitator comprising at least one Lewis acid and at least one reaction promoter, sufficient amounts of a compound of Formula III:
wherein X is independently a halide such as fluorine, chlorine, bromine or iodine and Ar 1 and Ar 2 are the same or different and each is a radical of a compound of Formula II; with a compound of Formula IV:
wherein R 1 , R 2 , R 3 , R 4 , and R 5 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbons atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthalene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, optionally with either of R 3 and R 4 , or R 4 and R 5 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, and Y is a direct bond, O, NR″, or SR″, wherein R″ is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, for a sufficient time, at a suitable temperature and pressure to form the compound of Formula I.
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have found that by using a combination comprising of at least one Lewis acid and at least one reaction promoter, preferably combined to form a reaction facilitator, the reaction of a cyanuric halide with substituted or unsubstituted aromatic compounds can prepare triazine derived 2-halo-4,6-bisaryl-1,3,5-triazine compounds in higher yield, with higher selectivity, at a lower reaction temperature, and/or within shorter reaction times than previously known.
Even more surprising is the fact that the reaction facilitator has been used with excellent results. This approach is in stark contrast to the state of the prior art where the use of anhydrous Lewis acids alone has always been advocated for this reaction step. It has also been discovered that 2-halo-4,6-bisaryl-1,3,5-triazines of this invention can be further reacted, without isolation, with a variety of phenolic derivatives to form 2-(2-oxyaryl)-4,6-bisaryl-1,3,5-triazine. Furthermore, the reaction can be applied to a variety of aromatic compounds. The key reasons for the increase in selectivity and reactivity has been shown to be the use of the reaction promoter.
As used herein, the cyanuric halide is a compound of the Formula V:
where each X is independently a halide such as fluorine, chlorine, bromine, or iodine.
The term aromatic compound is to include compounds of the Formula II:
wherein R 6 , R 7 , R 8 , R 9 , and R 10 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbon atoms including substituted or unsubstituted biphenylene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, and optionally with either of R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , or R 9 and R 10 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring.
Preferred aromatic compounds include benzene, toluene, ethylbenzene, m-xylene, o-xylene, p-xylene, chlorobenzene, dichlorobenzene, mesitylene, isobutylbenzene, isopropylbenzene, m-diisopropyl benzene, tetralin, biphenyl, naphthalene, acetophenone, benzophenone, acetanilide, anisole, thioanisole, resorcinol, bishexyloxy resorcinol, bisoctyloxy resorcinol, m-hexyloxy phenol, m-octyloxy phenol, or a mixture thereof.
The term “phenolic compound” is to include compounds of the formula IV:
wherein R 1 , R 2 , R 3 , R 4 , and R 5 are the same or different and each is hydrogen, halogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, cycloalkyl of 5 to 25 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, aracyl of 6 to 24 carbons atoms, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthalene, OR, NRR′, CONRR′, OCOR, CN, SR, SO 2 R, SO 3 H, SO 3 M, wherein M is an alkali metal, R and R′ are the same or different and each is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms, optionally with either of R 3 and R 4 , or R 4 and R 5 , taken together being a part of a saturated or unsaturated fused carbocyclic ring optionally containing O, N, or S atoms in the ring, and Y is a direct bond, O, NR″, or SR″ wherein R″ is hydrogen, alkyl of 1 to 24 carbon atoms, haloalkyl of 1 to 24 carbon atoms, aryl of 6 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms, acyl of 1 to 24 carbon atoms, cycloalkyl of 1 to 24 carbon atoms, cycloacyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, or aracyl of 6 to 24 carbons atoms.
Preferred phenolic compounds are substituted or unsubstituted monohydroxybenzene, monalkoxybenzene, dihydroxybenzene, dialkoxybenzene, hydroxyalkoxybenzene, trihydroxybenzene, trialkoxybenzene, hydroxybisalkoxybenzene, and bishydroxyalkoxybenzene. More preferred phenolic compounds are: resorcinol (1,3-dihydroxybenzene); C-alkylated resorcinols, e.g., 4-hexylresorcinol; mono-O-alkylated resorcinols, e.g., 3-methoxyphenol, 3-octyloxyphenol, 3-hexyloxyphenol, etc.; di-O-alkylated resorcinols, e.g., 1,3-dimethoxybenzene, 1,3-dioctylbenzene, 1,3-dihexyloxybenzene; C-alkylated-di-O-alkylated resorcinols, e.g., 4-hexyl-1,3-dimethoxybenzene; other polyhydroxy, polyalkoxy, hydroxy-alkoxy aromatics, e.g., 1,3,5-trihydroxybenzene, 1,3,5-trialkoxybenzene, 1,4-dihydroxybenzene, 1-hydroxy-4-alkoxybenzene, or mixtures thereof.
The term “Lewis acid” is intended to include aluminum halides, alkylaluminum halides, boron halides, tin halides, titanium halides, lead halides, zinc halides, iron halides, gallium halides, arsenic halide, copper halides, cadmium halides, mercury halides, antimony halides, thallium halides, zirconium halides, tungsten halides, molybdenum halides, niobium halides, and the like. Preferred Lewis acids include aluminum trichloride, aluminum tribromide, trimethylaluminum, boron trifluoride, boron trichloride, zinc dichloride, titanium tetrachloride, tin dichloride, tin tetrachloride, ferric chloride, or a mixture thereof.
As used herein the term “reaction promoter” is understood to comprise a compound which is used in combination with the Lewis acid to facilitate the reaction. Thus, triazine compounds are produced at lower reaction temperatures, greater yields, or higher selectivities compared to the use of the Lewis acid alone. Suitable reaction promoters include acids, bases, water, alcohols, aliphatic halides, halide salts, acid halides, halogens, alkenes, alkynes, ester, anhydride, carbonate, urethane, carbonyl, epoxy, ether, acetal compounds, or mixtures thereof.
Suitable alcohol compounds include carbon compounds of C 1 -C 20 , straight chain or branched, saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic, which has at least one hydroxyl group and which optionally contains at least one halide, thiol, thiol ether, amines, carbonyl, esters, carboxylic acids, amide, etc. Suitably alcohols include methanol, ethanol, propanol, butanol, isobutanol, t-butanol, 1,2-ethanediol, 3-chloro-1-propanol, 2-hydroxyl-acetic acid, 1-hydroxyl-3-pentanone, cyclohexanol, cyclohexenol, glycerol, phenol, m-hydroxyl-anisole, p-hydroxyl-benzylamine, benzyl alcohol, etc.
Suitable acid compounds include any inorganic or organic acid that contains at least one acidic proton, which may or may not be dissolved in an aqueous or organic solution. The organic acids include any organic compound that contains at least one acidic functional group including RCO 2 H, RSO 3 H, SO 2 H, RSH, ROH, RPO 3 H, RPO 2 H, wherein R is as defined above. Preferred protic acids include HCl, HBr, HI, HNO 3 , HNO 2 , H 2 S, H 2 SO 4 , H 3 PO 4 , H 2 CO 3 , acetic acid, formic acid proprionic acid, butanoic acid, benzoic acid, phthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, methanesulfonic acid, and p-toluenesulfonic acid or mixtures thereof.
Suitable aliphatic halides include C 1 -C 20 hydrocarbon compounds, saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic, that are substituted with at least one halide. Optionally, the aliphatic halide may be substituted in one or more positions with an hydroxyl, an ether, a polyether, a thiol, a thioether, an amine, such as —NHR, —NR′ 2 , —NRR′, a carboxylic acid, an ester, an amide or a carbon structure of C 1 -C 20 group which may be saturated or unsaturated and cyclic or non-cyclic, aromatic and which optionally may be substituted with any of the above preceding groups or mixtures thereof.
Specific aliphatic halide compounds that are suitable include carbon tetrachloride, chloroform, methylene chloride, chloromethane, carbon tetrabromide, tert-butylchloride, bromoform, dibromomethane, bromomethane, diiodomethane, iodomethane, dichloroethane, dibromoethane, chloroethanol, bromoethanol, benzyl chloride, benzyl bromide, ethanolamine, chloroacetic acid, bromoacetic acid or mixtures thereof.
The bases that are suitable include inorganic or organic bases dissolved either in water, an organic solvent, or a mixture of solvents. Inorganic bases include LiOH, NaOH, KOH, Mg(OH) 2 , Ca(OH) 2 , Zn(OH) 2 , Al(OH) 3 , NH 4 OH, Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , MgCO 3 , CaCO 3 , ZnCO 3 , (Al) 3 (CO 3 ) 2 , (NH 4 ) 3 CO 3 , LiNH 2 , NaNH 2 , KNH 2 , Mg(NH 2 ) 2 , Ca(NH 2 ) 2 , Zn(NH 2 ) 2 , Al(NH 2 ) 3 , or a mixture thereof. Organic bases include hydrocarbon compounds with C 1 -C 9 cyclic or non-cyclic that contain at least one alkoxide, amine, amide, carboxylate, or thiolate and which may be substituted in one or more positions with a halide, an hydroxyl, an ether, a polyether, a thiol, a thioether, an amine, such as —NHR, —NR′hd 2 , —NRR′, a carboxylic acid, an ester, or an amide. Organic bases include CH 3 O − , CH 3 CH 2 O − , CH 3 CH 2 CH 2 O − , (CH 3 ) 2 CHO − , ((CH 3 ) 2 CH) 2 CHO − , CH 3 CH 2 CH 2 CH 2 O − , (CH 3 ) 3 CO − , CH 3 NH 2 , CH 3 CH 2 NH 2 , CH 3 CH 2 CH 2 NH 2 , (CH 3 ) 2 CHNH 2 , ((CH 3 ) 2 CH) 2 CHNH 2 , CH 3 CH 2 CH 2 CH 2 NH 2 , (CH 3 ) 3 CNH 2 , (CH 3 ) 2 NH, (CH 3 CH 2 ) 2 NH, (CH 3 CH 2 CH 2 ) 2 NH, ((CH 3 ) 2 CH) 2 NH, (((CH 3 ) 2 CH) 2 CH) 2 NH, (CH 3 CH 2 CH 2 CH 2 ) 2 NH, ((CH 3 ) 3 C) 2 NH, (CH 3 ) 3 N, (CH 3 CH 2 ) 3 N, (CH 3 CH 2 CH 2 ) 3 N, ((CH 3 ) 2 CH) 3 N, (((CH 3 ) 2 CH) 2 CH) 3 N, (CH 3 CH 2 CH 2 CH 2 ) 3 N, ((CH 3 ) 3 C) 3 N, CH 3 NH − , CH 3 CH 2 NH − , CH 3 CH 2 CH 2 NH − , (CH 3 ) 2 CHNH − , ((CH 3 ) 2 CH) 2 CHNH − , CH 3 CH 2 CH 2 CH 2 NH − , (CH 3 ) 3 CNH − , (CH 3 ) 2 N − , (CH 3 CH 2 ) 2 N − , (CH 3 CH 2 CH 2 ) 2 N − , ((CH 3 ) 2 CH) 2 N − , (((CH 3 ) 2 CH) 2 CH) 2 N − , (CH 3 CH 2 CH 2 CH 2 ) 2 N − , pyrrolidine, piperidine, pyrrole, pyridine, aniline, tetramethylenediamine, the corresponding deprotonated amine, and a cation were appropriate. Organic bases also includes salts of deprotonated carboxylic acids such as salts of formate, acetate, propylate, butanoate, benzoate, with Li, Na, K, Mg, Ca, Al, Zn, or any other suitable cation. Organic base includes mixtures of the aforementioned inorganic and organic bases, or a mixture thereof.
Halogen reaction promoters include fluorine, chlorine, bromine, iodine, or mixed halogens dissolved in either water, an organic solvent, or a mixture of solvents or present as part of an organic or inorganic compound. Halogenated solvents that are suitable include dichloromethane, chloroform, carbon tetrachloride, dibromomethane, bromoform, iodomethane, diiodomethane, dichloroethane, 1,1,2,2-tetrachloroethane, benzene, toluene, acetone, acetic acid, hexane, or a mixture thereof.
Additional reaction promoters that are suitable include hydrocarbon compounds of Formula VI:
wherein R 11 and R 12 are either the same or different, may be taken together, hydrogen, hydrocarbon C 1 -C 20 , saturated or unsaturated, aromatic or non-aromatic, cyclic or non-cyclic, hydroxyl, ether, amine, substituted amine, carboxylate, ester, amide, and may be substituted at least once with a halide, hydroxyl, amine, amide, thiol, thioether, carboxylate, or a carbon structure of C 1 -C 12 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups, or mixtures thereof.
Additional compounds of Formula VI include those wherein R 11 and R 12 are either the same or different, may be taken together, hydrocarbon C 1 -C 12 , saturated or unsaturated, cyclic or non-cyclic, hydroxyl, ether, amine, substituted amine, carboxylate, ester, amide, and may be substituted at least once with a halide, hydroxyl, amine, amide, thiol, thioether, carboxylate, or a carbon structure of C 1 -C 7 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups, including hydrocarbon compounds acetaldehyde, butyraldehyde, glutaric dialdehyde, crotonaldehyde, benzaldehyde, acetone, methyl vinyl ketone, acetophenone, cyclohexanone, 2-cyclohexen-1-one, methyl acrylate, acetic anhydride, crotonic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, dimethyl adipate, diethyl phthalate, dimethyl carbonate, ethylene carbonate, diphenyl carbonate, phenyl carbamate, benzyl carbamate, methyl carbamate, urethane, propyl carbamate, or mixtures thereof.
Suitable ether compounds as reaction promoters include hydrocarbon compounds C 2 -C 20 , saturated or unsaturated, aromatic or non-aromatic, cyclic or non-cyclic, that have at least one C—O—C bond, and optionally are substituted with at least one halide, hydroxyl, amine, thiol, thioether, carboxylic acid, ester, or a carbon structure of C 1 -C 12 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups or mixtures thereof.
Additional ether compounds are hydrocarbon compounds of C 2 -C 12 that have at least one C—O—C bond, saturated or unsaturated, aromatic or non-aromatic, cyclic or non-cyclic, and may be substituted at least once with a halide, hydroxyl, amine, ether, thiol, thioether, carboxylic acid, ester, or a carbon structure of C 1 -C 7 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups including hydrocarbon compounds dimethyl ether, isopropyl ether, dipropyl ether, tert-amyl methyl ether, tert-butyl ethyl ether, allyl phenyl ether, allyl propyl ether, 4-methoxyphenyl ether, 3,3-dimethyl oxetane, dioxane, tetrahydropyran, tetrahydro-4H-pyran-4-ol, ethylene oxide, propylene oxide, styrene oxide, glycidol, glycidyl methyl ether, glycidyl butyrate, glycidyl methacrylate, 1,2-epoxy-3-phenoxypropane, 1,2-epoxyhexane, 1-chloro-2,3-epoxypropane, diethyl acetal, 2,2-dimethoxypropane, 1,1-dimethoxycyclohexane, 2-hexenal diethyl acetal, 3-chloropropionaldehyde diethyl acetal, benzaldehyde dimethyl acetal, 1,1,3-trimethoxypropane, or a mixture thereof.
Alkene reaction promoters include hydrocarbon compounds C 2 -C 20 that include at least one C—C double bond or C—C triple bond, whether the compounds are cyclic, heterocyclic or non-cyclic, and where the compounds are optionally substituted at least once with a halide, hydroxyl, amine, ether, thiol, thioether, carboxylic acid, ester, or a carbon structure of C 1 -C 12 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups, or mixtures thereof.
Additional alkene reaction promoters include hydrocarbon compounds of C 2 -C 12 with at least one C—C double bond or C—C triple bond, cyclic, heterocyclic or non-cyclic, and may be substituted at least once with a halide, hydroxyl, amine, ether, thiol, thioether, carboxylic acid, ester, or a carbon structure of C 1 -C 7 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups including hydrocarbon compounds 2-methylpropene, 1-butene, 2-butene, 2-methyl-2-butene, 1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 2-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-2-pentenoic acid, 3-methyl-1-penten-3-ol, 5-chloro-1-pentene, 4-bromo-2-methyl-2-butene, 1,4-pentadiene, 2,6-heptadienoic acid, hexatriene, cyclohexene, cyclohexadiene, cyclopentadiene, 2-cyclopenten-1-one, 2-methylfuran, styrene, methylstyrene, methyl vinyl ketone, acrylic acid, methyl acrylate, 1-pentyne, 2-pentyne, 2-pentyn-1-ol, 6-chloro-1-hexyne, 1,6-heptadiyne, or mixtures thereof.
Further reaction promoters include compounds of the formula RCOX, RSOX, RSO 2 X, or RPOX wherein at least one carbon, sulfur, or phosphorus atom is double bonded with at least one oxygen atom or phosphorous halides such as PX 3 and PX 5 wherein X is at least one halide from the group F, Cl, Br, and I. R is at least one halide or hydrocarbon C 1 -C 20 saturated or unsaturated, cyclic or non-cyclic, and may be substituted at least once with a halide, hydroxyl, amine, ether, thiol or mixtures thereof.
Compounds where R includes chloro, bromo, methyl, ethyl, propyl, isopropyl, butyl, phenyl, tolyl, naphthalyl, X includes F, Cl, Br, I, including compounds such as thionyl chloride, thionyl bromide, phosphorus oxybromide, phosphorus oxychloride, phosgene, acetyl chloride, acetyl bromide, benzoyl chloride, benzoyl bromide, toluoyl chloride, toluenesulfonyl chloride, terephthaloyl chloride, terephthaloyl bromide, oxalyl dichloride, oxalyl dibromide, succinyl dichloride, glutaryl dichloride, adipoyl dichloride, pimeloyl dichloride, methanesulfonyl chloride, ethanesulfonyl chloride, propanesulfonyl chloride, isopropylsulfonyl chloride, butanesulfonylchloride, benzenesulfonyl chloride, methyl dichlorophosphite, phosphoric acid halides, PCl 3 , PBr 3 , PCl 5 , PBr 5 , or mixtures thereof are suitable.
Compounds of the formula M a X b are also suitable reaction promoters, wherein the bond dissociation energy of M—X is about less than 145 kcal/mol at 298° Kelvin and where M includes at least one metal or organic cation of the formula NR 4 + , SR 3 + , or PR4 + where R includes C 1 -C 6 which may be substituted at least one halide, hydroxyl, amine, ether, thiol or mixtures thereof and where X is at least one anion.
Inorganic or organic compounds defined above that are suitable are also soluble in water or organic solvents such as methanol, ethanol, isopropanol, methylene chloride, acetone, diethyl ether, tetrahydrofuran, ethylene glycol, xylene, and chlorobenzene. These compounds include antimony halides, arsenic halides, barium halides, beryllium halides, bismuth halides, boron halides, cadmium halides, calcium halides, cerium halides, cesium halides, cesium tetrachloroaluminates, cobalt halides, copper halides, gold halides, iron halides, lanthanum halides, lithium halides, lithium tetrachloroaluminates, magnesium halides, manganese halides, mercury halides, nickel halides, osmium halides, phosphorus halides, potassium halides, potassium hydrogen fluorides, potassium tetrachloroaluminates, rhodium halides, samarium halides, selenium halides, silver halides, sodium halides, tin halides, lanthanum halides, sodium hydrogen fluorides, sodium tetrachloroaluminates, sodium/potassium tetracloroaurates, sodium/potassium/lithium/zinc/copper tetrafluoroborates, thalium halides, titanium chloride-aluminum chlorides (x:y), titanium halides, yttrium halides, zinc halides, zirconium halides, ammonium halides, tetraalkyl quaternary ammonium halides, aralkyl trialkylquaternary ammonium halides, arayl trialkylammonium halides, alkyl N-alkylimidazolium halides, aralkyl N-alkylimidazolium halides, alkyl N-aralkylimidazolium halides, N-alkylpyridinium halides, N-alkylisoquinolinium halides, N-alkylquinolinium halides, triphenylphosphonium halides, haloalkyl triphenylphosphonium halides, carboxyalkyl triphenylphosphonium halides, carbalkoxyalkyl triphenylphosphonium halides, cycloalkyl triphenylphosphonium halides, alkenyl triphenylphosphonium halides, aralkyltriphenylphosphonium halides, hydroxyaralkyl phosphonium halides, tetraphenylphosphonium halides, trialkylsulphonium halides, including but not limited to, inorganic compounds where M includes Li + , Na + , K + , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ti 4+ , Co 2+ , Ni 2+ , Cu + , Cu 2+ , Sn 2+ , Pb 2+ , Pb 4+ , Ce 3+ , and Ce 4+ ; organic compounds where M includes + N(CH 3 ) 4 , + N(CH 2 CH 3 ) 4 , + N(CH 2 CH 2 CH 3 ) 4 , + N(CH 2 CH 2 CH 2 CH 3 ) 4 , + NPh 4 , + P(CH 3 ) 4 , + P(CH 2 CH 3 ) 4 , + P(CH 2 CH 2 CH 3 ) 4 , + P(CH 2 CH 2 CH 2 CH 3 ) 4 , + PPh 4 , + S(CH 3 ) 3 , + S(CH 2 CH 3 ) 3 , + S(CH 2 CH 2 CH 3 ) 3 , + S(CH 2 CH 2 CH 2 CH 3 ) 3 , + SPh 3 , pyridinium, imidazolium, pyrrolidinium, and pyrrolium, and X includes inorganic X includes Cl − , Br − , I − , S 2− , O 2− , CO 3 2− , SO 3 2− , SO 4 2− , NO 2 − , NO 3 − , BF 4 − , OH − , PO 3 2− , PO 4 2− , ClO 4 − , MnO 4 − ; organic X includes HCO 2 − , CH 3 CO 2 − , CH 3 − , CH 3 CH 2 − , Ph − , CH 3 O − , CH 3 CH 2 O − , PhO − , CH 3 S − , CH 3 CH 2 S − , PhS − , CH 3 NH − , CH 3 CH 2 NH − , PhNH − or mixtures thereof.
The reaction promoter may also be water alone or as an aqueous solution or aqueous suspension, that contains other components therein, such as one or more of the promoters mentioned above.
Optionally, a combination of at least one Lewis acid and at least one reaction promoter, i.e. a reaction facilitator, is prepared before being added to the reactants.
The term “solvent” includes hydrocarbon compounds C 1 -C 24 saturated or unsaturated, cyclic or non-cyclic, aromatic or non-aromatic, optionally substituted with at least one halide, nitro, or sulfide group. Preferred solvents are hydrocarbons C 1 -C 8 , saturated or unsaturated, such as nitroalkanes, heptane, cyclohexane, benzene, nitrobenzene, dinitrobenzene, toluene, xylene, 1,1,2,2-tetrachloroethane, dichloromethane, dichloroethane, ether, dioxane, tetrahydrofuran, benzonitriles, dimethylsulfoxide, tetramethylene sulfone, carbon disulfide, and benzene rings substituted with at least one halide such as chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, difluorobenzene, trifluorobenzene, bromobenzene, dibromobenzene, tribromobenzene, or mixtures thereof.
The products of the present process include halo-bisaryl-1,3,5-triazine compounds or trisaryl-1,3,5-triazine compounds wherein the aromatic compounds include a C 5 -C 24 unsaturated ring, such as cyclopentadiene, phenyl, biphenyl, indene, naphthalene, tetralin, anthracene, phenanthrene, benzonaphthene, fluorene, which may be substituted in one or more positions with a halide, an hydroxyl, an ether, a polyether, a thiol, a thioether, an amine, such as —NHR,-NR 2 , —NRR′, a carboxylic acid, an ester, an amide or a C 1 -C 12 group which may be saturated or unsaturated and cyclic or non-cyclic, and which optionally may be substituted with any of the above preceding groups. A general structure of useful compounds is shown above in Formulas I and III.
Preferred products include chloro-bisaryl-1,3,5-triazine compounds or trisaryl-1,3,5-triazine compounds wherein the aromatic substituents include phenyl, an ortho, meta, and/or para substituted phenyl ring, a naphthalene ring substituted at one or more positions, substituted or unsubstituted biphenyl, or tetralin ring substituted at one or more positions, wherein the substitution group is a lower alkyl such as methyl, ethyl, propyl, butyl, isobutyl, t-butyl, pentyl, hexyl, septyl, octyl, nonyl, hydroxy, an ether group such as methoxy, ethoxy, propyloxy, octyloxy, nonoxy, or a halogen, such as fluoride, chloride, bromide, or iodide.
Other suitable products include chloro-bisaryl-1,3,5-triazine compounds, trisaryl-1,3,5-triazine compounds, or 2-(2-oxyaryl)-4,6-bisaryl-1,3,5-triazine compounds wherein the aromatic substituted compounds include o-xylene, m-xylene, p-xylene, o-cresol, m-cresol, p-cresol, mesitylene, trimethylbenzene, cumene, anisole, ethoxybenzene, benzene, toloune, ethylbenzene, biphenyl, tert-butylbenzene, propoxybenzene, butoxybenzene, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, o-ethoxyphenol, m-ethoxyphenol, p-ethoxyphenol, o-nonoxyphenol, m-nonoxyphenol, tetralin, 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-(4-alkoxy-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-chloro-4,6-bisphenyl-1,3,5-triazine; 2-(2,4-dihydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine; 2-(4-alkoxy-2-hydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine; 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and 2-(2-hydroxy-4-isooctyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
The term “step-wise” means a reaction sequence wherein a series of reactions are conducted, the first reaction producing a compound of Formula III and being carried out to about 50% to about 100% completion prior to addition of a compound of Formula IV to produce a compound of Formula I. Preferably the reaction is carried out to about 70% to about 100% completion prior to addition of compound of Formula IV, and more preferably to about 75% to about 100% completion.
The term “continuous” means a reaction sequence not defined as “step-wise.”
The relative amounts of the reactants are as follows. The amount of a cyanuric halide should be in sufficient amounts to react with aromatic compounds of Formula II to produce either 2-halo-4,6-bisaryl-1,3,5-triazine or 2,4,6-trisaryl-1,3,5-triazine. The amount of aromatic compound of Formula II is important to ensure that a sufficient amount of monohalo-bisaryl-triazine is synthesized without excessive amounts of undesired side products such as 2,4-dihalo-6-aryl-1,3,5-triazine or trisaryl triazine. Moreover, excess amounts of aromatic compounds can lead to undesired product distributions enriched in mono- and tris-aryl triazines, thus, making product separation and purification difficult and resource consuming.
The amount of aromatic compounds should be in sufficient amounts to synthesize 2-halo-4,6-bisaryl-1,3,5-triazine, 2,4,6-trisaryl-1,3,5-triazine, or convert 2-halo-4,6-bisaryl-1,3,5-triazine into 2,4,6-trisaryl-1,3,5-triazine. Preferably, there should be between about 1 to about 5 mol equivalents of aromatic compound of Formula II to cyanuric halide. More preferably, the amount of aromatic compound of Formula IV should be between about 0.5 to about 2.5 mol equivalents of aromatic compound of Formula IV to cyanuric halide. In some cases aromatic compounds of Formula II can be used both as a reactant and a solvent.
The amount of Lewis acid used in the reaction facilitator should be in sufficient amounts to transform 2,4,6-trihalo-1,3,5-triazine to the preferred 2-halo-4,6-bisaryl-1,3,5-triazine or 2,4,6-trisaryl-1,3,5-triazine. The amount of Lewis acid should be between about 0.5 to about 500 mol equivalents. Preferably, the amount of Lewis acid should be between about 1 to about 10 mol equivalents to cyanuric halide.
The amount of reaction promoter used in the reaction facilitator should be in sufficient amounts to transform 2,4,6-trihalo-1,3,5-triazine, to the preferred 2-halo-4,6-bisaryl-1,3,5-triazine or convert 2-halo-4,6-bisaryl-1,3,5-triazine to the compound of Formula I. Preferably, the amount of reaction promoter should be between about 0.01 to about 5 mol equivalents to cyanuric halide.
The Lewis acid and reaction promoter preferably combine to form a reaction facilitator complex that can be prepared in situ or pre-formed prior to addition to the reagents. The Lewis acid and/or reaction promoter or reaction facilitator can be combined with either a compound of Formula II or compound of Formula IV or both in any manner. In situ reaction facilitator preparation comprises addition of at least one Lewis acid and at least one reaction promoter to a mixture of cyanuric halide, at least one aromatic compound of Formula II, and optionally solvent without regard to addition order. To prepare the reaction facilitator prior to addition to the reagents, i.e., the pre-formed method, Lewis acid and reaction promoter are combined and allowed to mix prior to addition, optionally in an inert solvent. Thereafter, the reaction facilitator is added to the reagents or vice versa, as desired and in any addition order. As used herein, one or more Lewis acids may be used, the first step and second step Lewis acid may be the same or different. Additionally, one or more reaction promoters may be used, the first step and second step reaction promoter may be the same or different. In the “continuous” process, the use of additional Lewis acid and reaction promoter is optional.
If the reaction facilitator is prepared using the pre-formed method, preferred mixing time of the Lewis acid and reaction promoter, prior to addition to the reagents, is between about 1 minute to about 10 hours, more preferred is between about 10 minutes to about 5 hours. The preferred mixing temperature of the Lewis acid and reaction promoter combination, prior to addition to the reagents, is between about −50° C. to about 100° C., more preferred is between about −10° C. to about 50° C.
The reaction should run for sufficient time, at a sufficient temperature and pressure to synthesize the desired triazine compound. The preferred reaction time for the synthesis of compounds of Formula III, i.e., the first step, is between about 5 minutes and about 48 hours, more preferred between about 15 minutes and about 24 hours. The preferred reaction time for the synthesis of compounds of Formula I, i.e., the second step, is between about 10 minutes and about 24 hours, more preferably between about 30 minutes and about 12 hours. The use of the reaction facilitator reduces the reaction time while improving the selectivity for mono-halo-bis-aryl products in the first step. The preferred reaction temperature for the first step is between about −50° C. and about 150° C., more preferred between about −30° C. and about 50° C. One advantage of using the reaction facilitator is the elimination of the need to heat the reaction mixture to increase the rate of reaction. Additionally, due to the use of the reaction facilitator, the reaction temperature can be maintained at about ambient or lower temperatures, thus increasing product selectivity. The reaction pressure is not critical and can be about 1 atm or higher if desired. An inert gas such as nitrogen or argon is preferred. The preferred reaction temperature for the second step is between about 0° C. and about 120° C., more preferred between about 20° C. and about 100° C.
The step-wise process comprises mixing cyanuric halide and the reaction facilitator with one or more of the desired aromatic compounds, preferably until the reaction is about 70% to about 100% completed. Thereafter, the product of Formula III is isolated. The second aromatic compound of Formula IV is added to the isolated product of Formula III along with Lewis acid and optionally reaction promoter or reaction facilitator to synthesize the trisaryl-triazine. The step-wise sequence allows for the isolation, purification, and storage of Formula III product prior to subsequent reaction with compounds of Formula IV.
The continuous reaction comprises allowing a cyanuric halide to react with one or more aromatic compounds of Formula II in the presence of the reaction facilitator preferably until the reaction is about 70% to about 100% complete. Thereafter, without isolating the product of Formula III, the second aromatic compound of Formula IV is allowed to react with the product of Formula III in the presence of optionally at least one second Lewis acid and optionally at least one second reaction promoter or reaction facilitator preferably until the reaction is about 70% to about 100% complete. The continuous reaction eliminates the need to isolate the intermediate product of Formula III or use of additional reagents such as solvents, and optionally Lewis acids, reaction promoters, or reaction facilitators. Moreover, the one-step process simplifies the synthetic reaction pathway such that no unnecessary handling or processing of the reaction mixture is required until the reaction is completed.
To synthesize compounds of Formula III using the pre-formed reaction facilitator method, the preferred addition time of the reaction facilitator to a reagent mixture is between about 5 minutes to about 5 hours, more preferred is between about 15 minutes to about 3 hours. The addition temperature of the reaction facilitator to a reagent mixture is between about −50° C. to about 150° C., preferred addition temperature is between about −30° C. to about 50° C., and more preferred addition temperature between about −20° C. to about 30° C.
To synthesize compounds of Formula I using the pre-formed reaction facilitator, the preferred addition temperature of the reaction facilitator to a reagent mixture is between about 0° C. to about 100° C., preferred addition temperature is between about 20° C. to about 80° C.
To synthesize compounds of Formula I, the preferred addition time of the compound of Formula IV to the reaction mixture is between about 5 minutes to about 10 hours, more preferred addition time is between about 10 minutes to about 5 hours, and most preferred addition time is between about 15 minutes to about 2 hours. The addition temperature of the compound of Formula IV to the reaction mixture is between about 0° C. to about 150° C., preferred addition temperature is between about 20° C. to about 100° C.
The reaction facilitator should be present in amounts sufficient to react with the number of halogens being substituted on the triazine compound. A range of between about 1 to about 10 mol equivalents of Lewis acid and a range of between about 0.01 to about 5 mol equivalents of reaction promoter can be used. The preferred Lewis acid is aluminum halide, most preferably aluminum chloride. A preferred amount of Lewis acid is between about 2 to about 4 mol equivalents to halo-triazine. A preferred amount of reaction promoter is between about 0.05 to about 2 mol equivalents to triazine or triazine derived compounds.
The invention provides several advantages over prior art process such as higher yields, greater selectivity of reaction products, higher reaction rates, and/or applicability of reaction conditions to various aromatic compounds. The present invention consistently provided yields in the range of about 70 to about 98%, based on cyanuric halide conversion, as determined by HPLC analysis. Additionally, the ratio of desired 2-halo-4,6-bisaryl-1,3,5-triazine to trisaryl-1,3,5-triazine consistently averaged about 70:30 or more. The reaction facilitator significantly increased reaction rates in comparison to state of the art with Lewis acids alone. Moreover, the reaction conditions provided high yield and selectivity for a variety of aromatic compounds regardless of the aromatic substituents.
The triazine compounds synthesized using the present process can be applied to a variety of applications such as those described in U.S. Pat. No. 5,543,518 to Stevenson et al. Col. 10-19, the content of which, as noted above, is expressly incorporated by reference herein.
The 2-chloro-4,6-bisaryl-1,3,5-triazines are not only important intermediates for the preparation of trisaryl triazine UV absorbers, but they are also valuable intermediates for a variety of other commercially important products, such as vat dyestuffs (GB 884,802), photographic material (JP 09152701 A2), optical materials (JP 06065217 A2), and polymers (US 706,424; DE 2053414, DE 1246238). These compounds are also of interest for medicinal applications (e.g., see: R. L. N. Harris, Aust. J. Chem., 1981, 34, 623-634; G. S. Trivedi, A. J. Cowper, R. R. Astik, and K. A. Thaker, J. Inst. Chem., 1981, 53(3), 135-138 and 141-144).
EXAMPLES
Certain embodiments and features of the invention are illustrated, and not limited, by the following working examples.
The reaction progress can be monitored by HPLC or TLC. Further product characterization may be done by LCMS, MS, NMR, UV, direct comparison with authentic examples, or analytical techniques which are well known in the art. A typical HPLC analysis of the samples is carried out as follows. The reaction mixture may, in some cases be a two-phase system, with a lower, viscous liquid layer which may contain most of the reaction products (as AlCl 3 complexes), and a supernatant, which may contain very little material. This supernatant can be often enriched in unreacted cyanuric chloride. In case of a two-phase system, it is important that both phases are sampled together in a representative fashion. For example, the mixture can be stirred rapidly and a sample taken from the middle of the mixture using a polyethylene pipette with the tip cut off. When pipetting the sample into a vial for work-up, it is important that the contents of the pipette be completely discharged. Since the two phases will separate into upper and lower layers, partial discharge may result in a sample enriched in the lower layer.
The reaction sample is discharged into a 4-dram vial containing either chilled 5% HCl, or a mixture of 5% HCl and ice. The precipitate can be extracted with ethyl acetate and the water layer can be pipetted off. The ethyl acetate layer is then washed with water. Finally, an approximately 10% solution of the ethyl acetate layer in acetonitrile is prepared for HPLC analysis.
Certain embodiments and features of the invention are illustrated, and not limited, by the following working examples.
Example 1
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine without a Reaction Promoter
Cyanuric chloride (1.84 g) was allowed to react with 1.9 eq of m-xylene and 2.5 eq (3.35 g) of AlCl 3 in 25 mL of chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h. Analysis by HPLC, after 2.5 h, showed that less than 8% of cyanuric chloride had reacted to form only 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine, no 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine were present. The reaction was allowed to continue at room temperature. After 24 hours, HPLC analysis showed about 51% cyanuric chloride conversion and formation of 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in the ratio of 95:5, respectively. No 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was detected.
Example 2
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine without a Reaction Promoter
Cyanuric chloride (1.84 g) was allowed to react with 2.05 eq of m-xylene and 2.5 eq (3.35 g) of AlCl 3 in chlorobenzene at 5° C. for 2 h and then at 15° C. for 5 h. Analysis by HPLC showed about 5% conversion of cyanuric chloride to 2,4-bischloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and no 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine. The reaction was allowed to continue at room temperature. After 22 hours, HPLC analysis showed about 55% cyanuric chloride conversion and formation of 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in the ratio of 96:4, respectively. The reaction was allowed to continue. After 72 hours at room temperature, a final HPLC analysis showed 99% cyanuric chloride conversion, formation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in the ratio of 78:22, and no 2,4-bischloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected.
Example 3
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.1 eq Resorcinol and 2.5 eq AlCl 3
Cyanuric chloride was allowed to react with 2.05 eq of m-xylene in chlorobenzene, in the presence of 2.5 eq of AlCl 3 and 0.1 eq of resorcinol. The reaction was carried out at about 5° C. for 2 h and then at room temperature for 5 h. Analysis by HPLC showed about 10% conversion of cyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine. After about 40 h at room temperature, HPLC analysis showed 99% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine present in a 78:22 ratio respectively, no 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected.
Example 4
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.2 eq Resorcinol and 2.5 eq AlCl 3 and Conversion to 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
Cyanuric chloride (1.84 g) was allowed to react with 1.9 eq of m-xylene, in the presence of 2.5 eq of AlCl 3 (3.35 g) and 0.2 eq of resorcinol, in 25 mL chlorobenzene at about 5° C. for 0.5 h and then at room temperature for 3 h. Analysis by HPLC showed about 14% conversion of cyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine. After about 13 h at room temperature, HPLC analysis showed 99% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 82:18, respectively. No 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine or resorcinol-containing products were detected.
To the reaction mixture was added an additional 0.9 eq resorcinol and the reaction mixture was heated at 80° C. for 1 h. HPLC analysis indicated the formation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a 79:21 ratio, with about 1% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. The process to make 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine was complete within 15 hours.
The heating was discontinued and the reaction mixture allowed to cool to room temperature. 2% ice-cold aqueous HCl was added with stirring to break the aluminum complexes. A yellow precipitate was formed. The reaction mixture was filtered, washed with water, and dried to give 3.65 g of crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 5
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 1 eq Resorcinol and 2.5 eq AlCl 3
Cyanuric chloride (1.84 g) was allowed to react with 2.05 eq of m-xylene, in the presence of 2.5 eq of AlCl 3 (3.35 g) and 1 eq of resorcinol, in 25 mL chlorobenzene at about 5° C. for 2 h and then at 15° C. for 4 h. Analysis by HPLC showed 70% conversion of cyanuric chloride, mainly to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a 59:41 ratio. Two minor components were also present, 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine (5%) and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (3%). The reaction mixture was allowed to warm to room temperature, and after about 16 h at room temperature, HPLC analysis showed 92% cyanuric chloride conversion, mainly to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (66%), 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (25%), 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (4.5%), and 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4-(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine (3%).
Example 6
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.5 eq Resorcinol and 2.5 eq AlCl 3
Cyanuric chloride was allowed to react with 2 eq of m-xylene, in the presence of 2.5 eq of AlCl 3 and 0.5 eq of resorcinol, in chlorobenzene at room temperature for about 22 h. Analysis of the reaction mixture by HPLC showed about 94% cyanuric chloride conversion, mainly to 2,4,6-tris(2,4-dimethylphenyl)1,3,5-triazine, 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 69:27:4.
Example 7
Synthesis of chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3 eq AlCl 3
A. Absence of a Reaction Promoter
Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in the presence of 3 eq of AlCl 3 , in chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h. An HPLC analysis showed about 3% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine; no 2-chloro-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine or 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was detected. After 24 h at room temperature, HPLC analysis showed about 33% conversion to cyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, formed in a 96:4 ratio respectively.
B. Effect of 0.2 eq of Resorcinol
Thereafter, 0.2 eq of resorcinol was added to the above reaction mixture, and the reaction mixture was further stirred at room temperature for 16 h. HPLC analysis showed 97% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in an 80:20 ratio respectively; no 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected.
Example 8
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.2 eq Resorcinol and 3 eq AlCl 3
Cyanuric chloride was allowed to react with 1.9 eq of m-xylene, in the presence of 3 eq of AlCl 3 and 0.2 eq of resorcinol, in chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h. An HPLC analysis after 3 h at room temperature showed about 20% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine. The reaction mixture was stirred overnight at room temperature. After 18 h, an HPLC analysis showed 97% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in an 81:19 ratio respectively; no 2,4-dichloro-6-(2,4-dimethylphenyl)1,3,5-triazine was detected.
To the reaction mixture was then added 0.9 eq of resorcinol, and the mixture was heated in an oil bath to 60° C. (oil bath temperature). After 5 h, analysis by HPLC showed the formation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (73%) and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (21%), with 3% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 9
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.2 eq Resorcinol and 2.75 eq AlCl 3
Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in the presence of 2.75 eq of AlCl 3 , and 0.2 eq of resorcinol in chlorobenzene at 5° C. for 0.5 h and then allowed to warm to room temperature. After a total of 18 h at room temperature, analysis by HPLC showed 98% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in an 81:19 ratio respectively; no 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected. The reaction mixture was then allowed to react with 0.9 eq of resorcinol at 60° C. for 5 h. HPLC analysis showed the formation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 77:21 with 1% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 10
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.2 eq Resorcinol and 1.8 eq AlCl 3
Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in the presence of 1.8 eq of AlCl 3 , and 0.2 eq of resorcinol in chlorobenzene at 5° C. for 0.5 h and then allowed to warm to room temperature. After 18 h at room temperature, HPLC analysis showed 84% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a 46:54 ratio. 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was the major product, and about 3% 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was also present.
The reaction was allowed to continue at room temperature. After 4 days, HPLC analysis showed 93% cyanuric chloride conversion, with the following product distribution: 75% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine; 17% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 4% 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and other resorcinol-containing components as minor products.
Example 11
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.144 eq Resorcinol and 1.8 eq AlCl 3
Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in the presence of 1.8 eq of AlCl 3 and 0.144 eq of resorcinol, in chlorobenzene at 5° C. for 0.5 hand then at room temperature for 3 h. The ratio of AlCl 3 to resorcinol was thus 12.5:1. An HPLC analysis after 65 hours at room temperature showed 91% cyanuric chloride conversion, with the following product distribution: 79% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine; 10% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; 8% 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; and other resorcinol-containing compounds as minor products.
Example 12
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.15 eq Resorcinol and 2.5 eq AlCl 3 in a Tetrachloroethane Solvent
Cyanuric chloride was allowed to react with 1.9 eq of m-xylene, in the presence of 0.15 eq of resorcinol and 2.5 eq of AlCl 3 , in 1,1,2,2-tetrachloroethane at room temperature for about 26 h. HPLC analysis showed about 95% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in an 87:13 ratio. The reaction mixture was allowed to react with an additional 0.9 eq of resorcinol for 4 h at 90° C. HPLC analysis showed 98.3% 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine conversion, and the ratio of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was 84:16.
Example 13
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.2 eq Resorcinol and 3 eq AlCl 3 in a Tetrachloroethane Solvent
Cyanuric chloride was allowed to react with 2.05 eq of m-xylene, in the presence of 3 eq of AlCl 3 and 0.2 of resorcinol, in chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h. The first step (conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine) was completed in less than 16 h, with more than 98% cyanuric chloride conversion as determined by HPLC analysis. 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine were formed in an 86:14 ratio; no other products were detected. The reaction mixture was allowed to react with additional resorcinol at 110° C. for 1.5 h. HPLC analysis showed a product mixture of 82% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 14% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2% 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine, with only 1.5% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 14
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using Methyl Alcohol with 3 eq AlCl 3
A two-neck round bottom flask was equipped with a reflux condenser, an argon inlet, a magnetic stirring bar and a glass stopper. Cyanuric chloride (3.7 g) and 50 mL of chlorobenzene were added. Next, 3 eq of AlCl 3 (8 g) at ice-bath temperature was added, followed by 0.4 mL of methyl alcohol. After 5 min, 1.9 eq of m-xylene was added. The cooling was removed, and the reaction mixture was stirred at room temperature. The reaction was complete within 20 h at room temperature, as indicated by HPLC which showed the absence of m-xylene and 97% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in an 83:17 ratio.
To the reaction mixture was added 1.1 eq of resorcinol, and the reaction mixture was heated at 85° C. for 4.5 h. HPLC analysis showed the formation of 78% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 19% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.6% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 1.4% 2,4,6-tris(2,4-dihydroxylphenyl)-1,3,5-triazine. The reaction was allowed to cool to room temperature, and 2% ice-cold aqueous HCl was added. A yellow precipitate was formed, separated by filtration, washed with water, and dried to yield 7.7 g of crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 15
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.2 eq Resorcinol and 2.5 eq AlCl 3 at 45° C.
Cyanuric chloride was allowed to react with 1.9 eq m-xylene, in the presence of 2.5 eq AlCl 3 and 0.2 eq resorcinol, in chlorobenzene at 45° C. HPLC analysis of the reaction after 4 h showed 95% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a 67:33 ratio respectively.
Example 16
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.2 eq Resorcinol and 2.5 eq AlCl 3 in a Dichlorobenzene Solvent
Cyanuric chloride was allowed to react with 2 eq m-xylene, in the presence of 2.5 eq AlCl 3 and 0.2 eq of resorcinol, in ortho-dichlorobenzene at 24° C. After about 21 h, an exotherm was observed. A sample was immediately taken. HPLC analysis of the sample showed 94% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in an 81:19 ratio. After the exotherm had subsided, the cyanuric chloride conversion had increased to 97.5%, and the 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine ratio was 79:21.
To this mixture was added 0.9 eq additional resorcinol, and the mixture was heated to 80° C. for 1 h. HPLC analysis of the reaction showed 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, with a 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(xylyl)-1,3,5-triazine ratio of 77:23, and about 2% unreacted bisaryl-chloro-triazine.
Example 17
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.2 eq Resorcinol and 2.5 eq AlCl 3 in a Dichlorobenzene Solvent
A. No Cooling during Exotherm
Cyanuric chloride was allowed to react with 2 eq m-xylene, in the presence of 2.5 eq AlCl 3 and 0.2 eq of resorcinol, in ortho-dichlorobenzene at 40° C. A 4° C. exotherm was observed after 4-5 h. HPLC analysis of the reaction at this point showed 96% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a 78:22 ratio.
B. With Cooling to 10° C. after 4 h
The reaction of part (A) was repeated. The exotherm began after 4 h. A sample was immediately taken, and the reaction was cooled to 10° C. HPLC analysis of the sample showed 96% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a 78:22 ratio. There was also some unreacted 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine at this point. After 1 h at 10° C., the cyanuric chloride conversion was 97%, no 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine was detected, and the ratio of 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was 83:17.
Example 18
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.2 eq Resorcinol and 3 eq AlCl 3 with 6.5% Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 and 0.2 eq of resorcinol in chlorobenzene, was added 6.5% (based on the weight of cyanuric chloride) of concentrated HCl at ice-bath temperature. An immediate reaction with AlCl 3 was observed, leading to its almost complete solvation of AlCl 3 . 1.9 eq of m-xylene was then added. Within 5 min the color changed from light yellow to dark yellow to orange and finally dark red. The cooling bath was removed and the reaction mixture was analyzed at this stage by HPLC. The HPLC analysis showed 99% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a 92:8 ratio. Thereafter, the reaction mixture was allowed to react with 1.1 eq of resorcinol and subsequently, heated between 85°-90° C. for 1 h. HPLC analysis of the reaction mixture showed 85.3% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 12.8% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 1.7% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 19
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3 eq AlCl 3 with 6.5% Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 6.5% (based on the weight of cyanuric chloride) of concentrated HCl at ice-bath temperature. Within 1.5 h, the HPLC analysis showed almost complete conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-(2,4-dimethylphenyl)-1,3,5-triazine, which were formed in a ratio of 91:9. Thereafter, the reaction mixture was allowed to react with 1.1 eq of resorcinol and subsequently heated at 85° C. for 1 h. HPLC analysis showed the formation of 83.3% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 14.9% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 1.7% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. No trisresorcinol-triazine or bisresorcinol-triazine products were detected.
Example 20
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3 eq AlCl 3 with 13% Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 , and 1.9 eq of m-xylene in chlorobenzene, was added 13% (based on the weight of cyanuric chloride) of concentrated HCl at ice-bath temperature. Within 30 min at room temperature, 97% of the cyanuric chloride had reacted, to produce 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 96:4; no side products were detected. Further stirring gave 99.5% cyanuric chloride conversion, with the ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine unchanged and no other products were detected. Thereafter, the reaction mixture was allowed to react with 1.1 eq of resorcinol at 85° C. for 1.5 h. HPLC analysis of the reaction mixture showed the formation of 92.7% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 5% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2.3% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
The product was isolated by treating the reaction mixture with cold 2% aqueous HCl. Precipitate was collected by filtration, washed with water, and dried to give 92% yield of crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. The actual yield should be even higher than 92%, since some of the product was lost during the sampling for a number of HPLC analyses done during the course of the reaction. HPLC analysis of the isolated crude 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine showed 92.4% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 5% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2.35% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 0.25% 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.
Example 21
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3 eq AlCl 3 with 13% Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 13% (based on the weight of cyanuric chloride) of concentrated HCl at ice-bath temperature. After addition of 1.9 eq of m-xylene and the reaction of cyanuric chloride with m-xylene was complete, as indicated by the absence of m-xylene by HPLC analysis, the reaction mixture was quenched with ice-cold 2% aqueous HCl at about 5° C. The reaction mixture was then extracted with methylene chloride. The organic layer was washed with water, dried over anhydrous sodium sulfate, and the solvent removed under reduced pressure to give a white solid (quantitative yield based on m-xylene, and 95% yield based on cyanuric chloride). HPLC analysis indicated the isolated white solid to consist of >96% pure 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 22
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 2.5 eq AlCl 3 with 13% Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride, 2.5 eq of AlCl 3 in chlorobenzene, was added 13% (based on the weight of cyanuric chloride) of concentrated HCl at ice-bath temperature. HPLC analysis after 1 h at room temperature showed 89% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 82:18. The reaction mixture was left stirring at room temperature overnight after which the complete conversion of cyanuric chloride was detected. The next sample analyzed by HPLC after 22 h at room temperature showed 94% cyanuric chloride conversion, and the ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine to be 43:57.
Example 23
Synthesis of 2-(2,4-dihydroxylphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 2.5 eq AlCl 3 with 6.5% Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride, 2.5 eq of AlCl 3 in chlorobenzene, was added 6.5% (based on the weight of cyanuric chloride) of concentrated HCl at ice-bath temperature. After 22 h at room temperature, 98% of the cyanuric chloride had reacted to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in a ratio of 90:10. The reaction mixture was allowed to react with 1.1 eq of resorcinol and subsequently heated to 85° C. for 1.5 h. HPLC analysis of the reaction mixture showed 85.4% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 11.4% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2.6% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 0.6% 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.
Example 24
Synthesis of 2-chloro-4,6-bistetralin-1,3,5-triazine
To a stirring mixture of 1 eq of cyanuric chloride (5 g., 0.027 mol) in chlorobenzene, maintained at ice bath temperature under nitrogen, was added 3 eq of AlCl 3 (10.87 g., 0.081 mol) over 5-10 min, followed by the addition of conc. HCl (0.54 mL, 0.0065 mol) over 5-10 min, taking care that the reaction temperature did not exceed 5° C. The reaction slurry was stirred at 0-5° C. for another 10 min. The reaction was cooled to −10° C. and tetralin (7.01 mL, 0.0516 mol) was added at −10° C. over 2 h. At the completion of the tetralin addition, the reaction mixture was stirred at −10° C. for 2 h. The reaction was warmed to 0° C. and stirred for 1 h. HPLC analysis of the reaction mixture showed 98.5% conversion of cyanuric chloride to 2-chloro-4,6-bistetralin-1,3,5-triazine and 2,4,6-tristetralin-1,3,5-triazine in a 92:8 ratio. The slurry was warmed to 40° C. and resorcinol (3.29 g, 0.0298 mol) was added and the reaction mixture was stirred at 80° C. for 2 h. HPLC analysis showed 100% conversion of 2-chloro-4,6-bistetralin-1,3,5-triazine to 2-(2,4-dihydroxyphenyl)-4,6-bistetralin-1,3,5-triazine.
Comparative Example 24
Synthesis of 2-chloro-4,6-bistetralin-1,3,5-triazine
To a stirring mixture of 1 eq of cyanuric chloride (5 g., 0.027 mol) in chlorobenzene (50 mL), maintained at ice bath temperature under nitrogen, was added 3 eq of AlCl 3 (10.87 g., 0.081 mol) over 5-10 min. The reaction slurry was stirred at 0-5° C. for another 10 min. The reaction was cooled to −10° C. and tetralin (7.01 mL, 0.0516 mol) was added at −10° C. over 2 h. At the completion of the tetralin addition, the reaction mixture was stirred at −10° C. for 2 h. The reaction was warmed to 0° C. and stirred for 1 h. HPLC analysis of the reaction mixture showed no reaction of cyanuric chloride, and no formation of 2-chloro-4,6-bistetralin-1,3,5-triazine.
Example 25
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3 eq AlCl 3 with Concentrated Sulfuric Acid
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 0.24 eq of concentrated H 2 SO 4 at ice-bath temperature. After 5 min of stirring 2 eq of m-xylene was added. After another 5 min, the cooling bath was removed and the reaction mixture was stirred at room temperature. HPLC analysis after 2 h at room temperature showed 100% of the cyanuric chloride had reacted to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in a ratio of 86:14.
Example 26
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3.5 eq AlCl 3 with 10% Aqueous Sulfuric Acid
To a stirring mixture of 1 eq of cyanuric chloride, 3.5 eq of AlCl 3 in chlorobenzene, was added 0.036 eq of sulfuric acid as a 10% aq. solution at ice-bath temperature. After 10 min of stirring 1.9 eq of m-xylene was added. After 5 min at ice bath temperature the reaction mixture was allowed to warm to 10° C. After 1 h 20 min. HPLC analysis showed 89% of the cyanuric chloride had reacted to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in a ratio of 89:11. HPLC analysis, after 3h at 9-11° C., showed 94% of the cyanuric chloride had reacted to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in a ratio of 95:5. HPLC analysis, after 5 h at 9-11° C. and 17 h at room temperature, showed 98.5% of the cyanuric chloride had reacted to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in a ratio of 97:3.
The reaction mixture was allowed to react with 1.1 eq of resorcinol and subsequently heated to 85° C. for 3 h. HPLC analysis of the reaction mixture showed 92.7% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 4% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2.4% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 0.9% 2,4,6-(2,4-dihydroxyphenyl)-1,3,5-triazine.
Example 27
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3 eq AlCl 3 with Benzoic Acid
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 0.24 eq of benzoic acid as a 4% solution in chlorobenzene at ice-bath temperature. m-Xylene (1.95 eq) was then added. After 5 min at ice bath temperature, the reaction was allowed to warm to room temperature. HPLC analysis after 22 h at room temperature, showed 99.5% of the cyanuric chloride had reacted to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, which were present in a ratio of 82:18.
Example 28
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3 eq AlCl 3 and 6.5% Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 0.24 eq of concentrated HCl at ice-bath temperature. After 45 min, 0.95 eq of m-xylene and 0.95 eq of toluene were added. After 45 min at ice bath temperature, the reaction was stirred at 9° C. for 1 h and then at room temperature for 2 h. HPLC analysis showed 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine as the major product with lesser amounts of 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine, and 2-chloro-4-(4-methylphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine.
The reaction mixture was allowed to react with 1.1 eq of resorcinol and subsequently heated to 85° C. for 2 h. HPLC analysis of the reaction mixture showed 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine as the major product with lesser amounts of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, and 2-(2,4-dihydroxyphenyl)-4-(4-methylphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine.
Example 29
Synthesis of 2-(2,4-dimethoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3 eq AlCl 3 with Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 0.24 eq of concentrated HCl at ice-bath temperature. After 10 min, 1.9 eq of m-xylene was added. The reaction was stirred at ice bath temperature for 2 h and then at room temperature for 5 h. HPLC analysis showed formation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine as the major product and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a 91:9 ratio. The reaction mixture was allowed to react with 1.1 eq of 1,3-dimethoxybenzene. The mixture was heated to 59-61° C. and stirred for 2 h, then heated 85° C. and stirred for 5 h. HPLC analysis of the reaction mixture showed 76% 2-(2,4-dimethoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 24% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (HPLC area percent at 290 nm) as the only products.
Example 30
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 2.5 eq AlCl 3 and 0.12 eq Anhydrous HCl
To a mixture of cyanuric chloride in chlorobenzene cooled to 5° C. was added 2.5 eq of AlCl 3 , 0.12 eq of anhydrous HCl (as a 0.28 N solution in chlorobenzene), and 1.9 eq of m-xylene. This mixture was warmed to 23° C. with stirring, and the progress of the reaction was monitored by HPLC. The data are given in Table I below.
TABLE 1
Reaction Profile for Anhydrous HCl
Cyanuric
Bis-xylyl-
chloride
Mono-xylyl-Bis-
monochloro-
Tris-xylyl-
Time (h)
Conversion (%)
chloro-Triazine
triazine
Triazine
1
3
100
2
6
100
3
9
100
25
65
58
40
2
The cyanuric chloride conversion is based on area percent at 210 nm. The amounts of the other components are based on area percent at 290 nm.
Example 31
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3 eq AlCl 3 and 0.2 eq Anhydrous HCl
To a mixture of cyanuric chloride in chlorobenzene cooled to 5° C. was added 3 eq of AlCl 3 , 0.2 eq of anhydrous HCl (as a 0.156 N solution in chlorobenzene), and 1.9 eq of m-xylene. This mixture was then warmed to 23° C. with stirring, and the progress of the reaction was monitored by HPLC. The data are given in Table II below.
TABLE II
Reaction Profile for Anhydrous HCl (0.20 eq)
Cyanuric
Chloride
Monoxylyl-
Bis-xylyl-
Bisxylyl-
Time
Conver-
bischloro-
monochloro-
Tris-xylyl-
monochloro:
(h)
sion (%)
triazine
triazine
triazine
Tris-xylyl*
1
2
100
2.5
6
100
4
15
97
3
5.5
19
97
3
23
59
89
10
1
94:6
48
88
0.5
65.5
34
78:22
*corrected ratio.
Example 32
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.2 eq Resorcinol and 3 eq AlCl 3 with 0.55 eq H 2 O
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 and 0.2 eq of resorcinol in chlorobenzene, was added 0.55 eq of water at ice-bath temperature. An immediate reaction with AlCl 3 was observed. After 10 min of stirring, 1.9 eq of m-xylene was added. After another 10 min, the cooling bath was removed and the reaction mixture was stirred at room temperature. HPLC analysis of the reaction mixture after 1.5 h at room temperature showed 84% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a 95:5 ratio respectively. After 2.5 h at room temperature HPLC analysis showed 95% conversion of cyanuric chloride, and a ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine of 94:6. Thereafter, 1 eq of resorcinol was added and the reaction mixture was stirred at 85° C. for 1 h. HPLC analysis of the reaction mixture showed 89.4% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 7.7% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.6% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 1.3% 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.
Example 33
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3 eq AlCl 3 with 0.55 eq Water
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene, was added 0.55 eq of water at ice-bath temperature. After 10 min 1.9 eq of m-xylene was added. HPLC analysis after 30 min at room temperature showed 93% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 94:6 respectively. After 1 h at room temperature HPLC analysis showed 98% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 92:8. After 4.5 h at room temperature, HPLC analysis showed conversion of cyanuric chloride had increased to 99%, and the ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was 93:7.
Thereafter, 1.1 eq of resorcinol was added and the mixture stirred at 85° C. for 2 h. HPLC analysis of the reaction mixture showed 91.1% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 6.3% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.8% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 0.75% 2,4,6-tris(2,4-dihydroxyphenyl)-1,3,5-triazine.
Example 34
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 2.5 eq AlCl 3 with 0.55 eq Water
To a stirring mixture of 1 eq of cyanuric chloride, 2.5 eq of AlCl 3 in chlorobenzene, was added 0.55 eq of water at ice-bath temperature. Analysis by HPLC, after 30 min at room temperature, showed 92% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 94:6. After 1 h at room temperature, HPLC analysis of the reaction mixture showed 96% conversion of cyanuric chloride, and a ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine of 88:12. After 4.5 h at room temperature, HPLC analysis showed 97% conversion of cyanuric chloride and a ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine of 77:23.
Example 35
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3.25 eq AlCl 3 with 0.55 eq Water
To a stirring mixture of 1 eq of cyanuric chloride, 3.25 eq of AlCl 3 in chlorobenzene, was added 0.55 eq of water at ice-bath temperature. After 10 min 1.9 eq of m-xylene was added. Within 1 h, 98% conversion of cyanuric chloride was detected, based on HPLC analysis. The ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was 92:8. A final sample analysis after complete disappearance of m-xylene showed 99% cyanuric chloride conversion, and the ratio of the products, 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, was 89:11.
Example 36
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3 eq AlCl 3 without Promoter
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of AlCl 3 in chlorobenzene was added. After 10 min 1.9 eq of m-xylene was added. HPLC analysis after 2 h showed 5% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine. After 24 h at room temperature HPLC analysis showed 46% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in a 96:4.
Example 37
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3.25 eq AlCl 3 without Promoter
The cyanuric chloride was allowed to react with 2 eq of m-xylene in the presence of 3.25 eq of AlCl 3 in chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h. HPLC analysis. After 4 h, showed about 15% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine; no 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was detected. After 24 h at room temperature, HPLC analysis showed about 51% conversion of cyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, formed in a 91:9 ratio.
Example 38
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine Using 3.5 eq AlCl 3 without Promoter
The cyanuric chloride was allowed to react with 2 eq of m-xylene in the presence of 3.5 eq of AlCl 3 in chlorobenzene at 5° C. for 0.5 h and then at room temperature for 3 h HPLC analysis. After 4 h, showed about 6% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine; no 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine or 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine was detected. After 24 h at room temperature, HPLC analysis showed about 38% conversion of cyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, formed in a 96:4 ratio.
Example 39
Preparation of 2-(2,4-dihydroxyphenyl-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with Dichloromethane and 2.5 eq AlCl 3
To a stirring mixture of 1 eq of cyanuric chloride 0.4 eq of dichloromethane in chlorobenzene was added 2.5 eq of aluminum chloride at ice-bath temperature, the cooling bath was removed and the reaction mixture stirred at room temperature. The HPLC analysis after 3 h at room temperature showed 14% of cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine formed in a ratio of 93:7. After about 14 h at room temperature, HPLC analysis showed 98.5% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 87:13.
To the above reaction mixture, 1 eq of resorcinol was added and the mixture stirred at 80-85° C. for 1 h. HPLC analysis of the reaction mixture showed 76% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 14% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine.
Example 40
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with Dichloromethane Resorcinol and 2.5 eq Aluminum Chloride
To a stirring mixture of 1 eq of cyanuric chloride, 0.4 eq of dichloromethane, and 0.2 eq of resorcinol in chlorobenzene, was added 2.5 eq of aluminum chloride at ice-bath temperature, the cooling bath was removed and the reaction mixture stirred at room temperature. After 15 min, 1.9 eq of m-xylene was added and after 15 min of stirring at ice-bath temperature, the cooling bath was removed and the reaction mixture stirred at room temperature. HPLC analysis after 3 h at room temperature showed 95% of cyanuric chloride conversion to 2-chloro-4,6 bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine formed in a ratio of 92:8.
To the above reaction mixture, 1 eq of resorcinol was added and the mixture stirred at 80-85° C. for 1.5 h. HPLC analysis of the reaction mixture showed 80.5% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 9.9% of 2,4,6-tris(2,4-dimethylphenyl)1,3,5-triazine.
Example 41
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with 2.3 eq of Tert-butyl Chloride and 2.5 eq Aluminum Chloride
To a stirring mixture of 1 eq of cyanuric chloride and 2.5 eq of aluminum chloride in chlorobenzene at ice bath temperature was added 2.3 eq of tert-butyl chloride over 1 h. After 5 min. of stirring, 1.95 eq of m-xylene was added over 5 min. The ice bath was replaced with a water bath, and the reaction mixture was allowed to warmed to room temperature. After 5 min. at room temperature, HPLC analysis showed 97% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)1,3,5-triazine, present in a ratio of 98:2.
To the above reaction mixture was added 1.1 eq of resorcinol, and the mixture stirred at 80° C. for 3 h. HPLC analysis of the reaction mixture showed 94% of 2-(2,4-dihydroxyphenyl)-4,6 bis(2,4-dimethylphenyl)-1,3-triazine, 3.5% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2.5% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 42
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with 0.46 eq of Tert-butyl Chloride with 2.5 eq Aluminum Chloride
To a stirring mixture of 1 eq of cyanuric chloride and 2.5 eq of aluminum chloride in chlorobenzene at ice bath temperature was added 0.46 eq of tert-butyl chloride over 10 min. After 5 min. of stirring, 1.95 eq of m-xylene was added over 5 min. After 5 min., the ice bath was replaced with a water bath, and the reaction mixture warmed to room temperature. After stirring at room temperature for 22 h, HPLC analysis showed 98% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ratio of 84:16.
Example 43
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with 0.5 eq Tert-butylchloride, 0.2 Resorcinol and 2.5 eq Aluminum Chloride
To a stirring mixture of 1 eq of cyanuric chloride, 0.2 eq of resorcinol, and 2.5 eq of aluminum chloride in chlorobenzene at ice bath temperature was added 0.5 eq of tert-butyl chloride over 10 min. After 5 min. of stirring, 1.95 eq of m-xylene was added. The ice bath was replaced with a water bath, and the reaction mixture was allowed to warm to room temperature. After stirring at room temperature for 2 h, HPLC analysis showed 97% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ratio of 91:9.
To the above reaction mixture was added 1 eq of resorcinol, and the mixture stirred at 78-82° C. for 3 h. HPLC analysis of the reaction mixture showed 86% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 12% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 2% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 44
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using Sodium Hydroxide and 3 eq of Aluminum Chloride
To a stirring mixture of 3.7 g (1 eq) of cyanuric chloride, 8 g (3 eq) of aluminum chloride in 50 mL chlorobenzene, was added 0.4 mL of aqueous sodium hydroxide solution (50%) at ice-bath temperature. After 10 min of stirring, 1.9 eq of m-xylene was added. The cooling bath was removed and the reaction mixture stirred at room temperature. HPLC analysis after 30 min at room temperature showed 91% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of 96:4. A second sample analyzed after 1 h at room temperature showed 94% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylpheny)-1,3,5-triazine, in a ratio of 92:8. After a total of 4 h at room temperature, HPLC analysis showed 95% conversion of cyanuric chloride and a ratio of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine of 89:11.
To the above reaction mixture, 1.1 eq of resorcinol was added and the mixture heated with stirring at 80° C. for 2 h. HPLC analysis of the reaction mixture showed 80% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 16% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.5% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2.2% of 2,4,6-tris(2,4-dihydroxylphenyl)-1,3,5-triazine.
Example 45
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using Aluminum Hydroxide with 3 eq Aluminum Chloride
To a stirring mixture of 3.7 g (1 eq) of cyanuric chloride, 8 g (3 eq) of aluminum chloride in 50 mL chlorobenzene was added 0.39 g (0.5 eq) of aluminum hydroxide at ice-bath temperature. After 10 min of stirring, 1.9 eq of m-xylene was added. The cooling bath was removed after 10 min and the reaction mixture stirred at room temperature. HPLC analysis after 20 h at room temperature showed 98% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of 80:20.
To the above reaction mixture, 1.1 eq of resorcinol was added and the mixture heated with stirring at 80° C. for 2 h. HPLC analysis of the reaction mixture showed 74% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 22% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1.5% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 1.4% of 2,4,6-tris(2,4-dihydroxylphenyl)-1,3,5-triazine.
Example 46
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using aq. Ammonium Hydroxide with 3 eq Aluminum Chloride
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at ice bath temperature was added 0.38 eq of aq. ammonium hydroxide over 15 min. After 15 min. of stirring, 1.95 eq of m-xylene was added. The ice bath was replaced with a water bath, and the reaction mixture was allowed to warm to room temperature. After 4 h at room temperature, HPLC analysis showed 97% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ratio of 89:11. After an additional 1 h at room temperature, the cyanuric chloride conversion was >99%% and the 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine to 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine ratio was at 89:11.
To the above reaction mixture was added 1.1 eq of resorcinol, and the mixture stirred at 78-82° C. for 3 h. HPLC analysis of the reaction mixture showed 84% of 2-(2,4-dihydroxylphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 12% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 47
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using Sodium Methoxide and 3 eq Aluminum Chloride
To a stirring mixture of 3 eq of aluminum chloride in chlorobenzene at ice bath temperature was added 0.5 eq of sodium methoxide over 15 min. The reaction mixture was warmed to room temperature for 0.5 h and then cooled back to ice bath temperature. To the reaction mixture was added 1 eq of cyanuric chloride and 1.95 eq of m-xylene. The ice bach was replaced with a water bath, and the reaction mixture warmed to room temperature. After 7.5 h at room temperature, HPLC analysis showed 98% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ratio of 75:25.
To the above reaction mixture was added 1.1 eq of resorcinol, and the mixture stirred at 85° C. for 4 h. HPLC analysis of the reaction mixture showed 80% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 18% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine and 2% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 48
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using α-methylstyrene with 3 eq Aluminum Chloride
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of aluminum chloride in chlorobenzene was added 0.5 eq of α-methylstyrene at ice-bath temperature. After 10 min of stirring, 1.9 eq of m-xylene was added. After another 10 min, the cooling bath was removed and the reaction mixture was stirred at room temperature. HPLC analysis after 16 h at room temperature showed 96% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine (tris-xylyl triazine), formed in a ratio of 73:27.
Example 49
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with 3 eq Aluminum Chloride without Promoter
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of aluminum chloride in chlorobenzene was added at ice-bath temperature. After addition of m-xylene, the reaction mixture was allowed to stir at room temperature for a total of 24 h. HPLC analysis of the reaction mixture showed about 46% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of 96:4.
Example 50
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with Butyryl Chloride and 3 eq Aluminum Chloride
To a stirring mixture of 1 eq of cyanuric chloride, 3 eq of aluminum chloride in chlorobenzene was added 0.5 eq of butyryl chloride at ice-bath temperature. After 10 min of stirring, 1.9 eq of m-xylene was added. After another 10 min, the cooling bath was removed and the reaction mixture was stirred at room temperature. HPLC analysis after 16 h at room temperature showed 92% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of 78:22.
Example 51
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using Pyridine Hydrochloride with 3.5 eq of Aluminum Chloride
To a stirring mixture of 1 eq of cyanuric chloride and 3.5 eq of aluminum chloride in chlorobenzene was added 0.5 eq of pyridine hydrochloride at ice-bath temperature. After 10 min of stirring, 1.9 eq of m-xylene was added. The reaction mixture was stirred for 1 h at ice bath temperature, 3.5 h at 10° C., and 6.5 h at 15-20° C. HPLC analysis showed 98% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-methylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, formed in a ratio of 88:12.
To the above reaction mixture was added 1.1 eq of resorcinol, and the mixture stirred at 85° C. for 3 h. HPLC analysis of the reaction mixture showed 86% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 13% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 1% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 52
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 3.5 eq Aluminum Chloride
To a stirring mixture of 1 eq of cyanuric chloride and 3.5 eq of aluminum chloride in chlorobenzene, after 10 min of stirring. 1.9 eq of m-xylene was added. HPLC analysis after 4 h at room temperature showed 6% cyanuric chloride conversion to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine with no formation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. The reaction mixture was stirred at room temperature for 24 h. HPLC analysis showed about 38% conversion of cyanuric chloride to 2,4-dichloro-6-(2,4-dimethylphenyl)-1,3,5-triazine and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, in a 96:4 ratio.
Example 53
Synthesis of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using Benzyltriethylammonium Chloride and Resorcinol and 2.5 eq Aluminum Chloride
To a stirring mixture of 1 eq of cyanuric chloride, 0.2 eq benzyltriethylammonium chloride, and 0.2 eq of resorcinol in chlorobenzene was added 2.5 eq of aluminum chloride at ice-bath temperature. After 10 min. of stirring, 1.9 eq of m-xylene was added. The reaction mixture was stirred for 1 hour at ice bath temperature, and 3 h at 18-20° C. HPLC analysis showed 72% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 86:14.
Example 54
Synthesis of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using Lithium Chloride with 3 eq of Aluminum Chloride
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene was added 0.5 eq of lithium chloride at ice-bath temperature. After 10 min. of stirring, 1.9 eq of m-xylene was added. The reaction mixture was allowed to stir at room temperature. HPLC analysis of the reaction mixture after 44 h of stirring at room temperature showed 97% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, in a ratio of 81:19.
To the above reaction mixture, 1.1 eq of resorcinol was added and the mixture stirred at 70° C. for 3 hours. HPLC analysis of the reaction mixture showed 76% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 20% of 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, 1% of unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2% of 2,4,6-tris(2,4-dihydroxylphenyl)-1,3,5-triazine.
Example 55
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
Part A: Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.50 eq of Allyl Bromide as Promoter
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at ice bath temperature was added 0.5 eq of allyl bromide over 20 min. An immediate reaction with aluminum chloride was observed during the addition. After 10 min at 0-1° C., 1.9 eq of m-xylene was added over 5 min. After 30 min at 0-1° C., the ice bath was replaced with a cold-water bath, and the reaction mixture was stirred at 17-19° C. for 25.5 h. HPLC analysis showed 95% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, present in a ration of 86:14. A small amount of by-product was detected, probably arising from the reaction of 2-chloro-4,6-(2,4-dimethylphenyl)-1,3,5-triazine (CDMPT) with allyl bromide, was observed. If this product is counted along with CDMPT itself, the bis-xylyl-mono-chloro-triazine to tris-xylyl-triazine ratio increases to 89:11.
Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2.4-dimethylphenyl)-1,3,5-triazine
To the above reaction mixture was added 1:1 eq resorcinol and the mixture was stirred at 85° C. for 17 h. HPLC analysis of the reaction mixture showed 87% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 13% 2,4,6-tris(2,4dimethylphenyl)-1,3,5-triazine.
Example 56
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
Part A: Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; Using 0.4 eq of 3-methyl-2-buten-1-ol as Promoter
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at −13° C. to −15° C. was added 0.4 eq of 3-methyl-2-buten-1ol over 15 min. An immediate reaction with aluminum chloride was observed during the addition. The mixture was allowed to warm to 0-1° C. and after stirring for 10 min, 1.9 eq of m-xylene was added over 10 min. After stirring for 2 h at 0-1° C., the ice bath was replaced with a cold-water bath and the reaction mixture was stirred at 15-16° C. for 18 h. HPLC analysis showed 94% of cyanuric chloride conversion to 2-chloro-4,6,-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 86:14.
Part B: Preparation of 2-(2 4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was stirred at 85° C. for 2 h. HPLC analysis of the reaction mixture showed 84% of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 14% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine, and 2% unreacted 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 57
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
Part A: Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.5 eq of Benzoyl Chloride as Promoter
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at 1-2° C. was added 0.5 eq of benzoyl chloride over 10 min. After stirring for 10 min, 1.9 eq of m-xylene was added over 6 min. After stirring for 2 h at 0-1° C., the ice bath was replaced with a cold water bath and the reaction mixture was allowed to warm to 15-16° C. and stirred for 19 h. HPLC analysis showed 84% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 86:14.
Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was stirred at 85° C. for 2 h. HPLC analysis of the reaction mixture showed 80% 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 20% 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine.
Example 58
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.5 eq of Propanesulfonyl Chloride as Promoter
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at 0-1° C. was added 0.5 eq of propanesulfonyl chloride over 10 min. An immediate reaction with aluminum chloride was observed during the addition. After stirring for 10 min at 1-2° C., 1.9 eq of m-xylene was added over 6 min. After stirring for 2 h at 0-2° C., the ice bath was replaced with a cold water bath, the reaction was allowed to warm to 16-18° C. and was stirred for 20 h. HPLC analysis showed 92% of cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 90:10.
Example 59
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.5 eq of p-toluenesulfonyl Chloride as Promoter
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at 0-2° C. was added 0.5 eq of p-toluenensulfonyl chloride over 10 min. After stirring for 10 min, 1.9 eq of m-xylene was added over 6 min. After stirring at 0-1° C., the ice bath was replaced with a cold water bath, the reaction mixture was allowed to warm to 16-17° C. and was stirred for 21 h. The water bath was removed and the temperature was allowed to warm to 23° C. HPLC analysis showed the conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 79:21.
Example 60
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using 0.5 eq of Acetic Anhydride as Promoter
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in chlorobenzene at 1-2° C. was added a solution of 0.5 eq of acetic anhydride in chlorobenzene over 10 min. An immediate reaction with aluminum chloride (exotherm) was observed during addition. After stirring for 10 min, 1.9 eq of m-xylene was added over 6 min. After stirring at 0-1° C. for 2 h, the ice bath was replaced with a cold water bath, the reaction mixture was allowed to warm to 16° C. and was stirred for 19 h. HPLC analysis showed the complete conversion of m-xylene, but only 72% conversion of cyanuric chloride to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine in a ratio of 84:16.
Example 61
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine
Part A: Preparation of 2-chloro-4,6-bisphenyl-1,3,5-triazine Using Concentrated HCl as a Reaction Promoter
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added concentrated HCl (13 wt % based on cyanuric chloride). After 10 minutes, 1.95 eq of benzene was added and the reaction mixture stirred at ice bath temperature for 10 minutes. The cooling bath was removed, the reaction was allowed to warm to room temperature, and stirred. After 26 h at room temperature, an HPLC analysis indicated about 86% cyanuric chloride conversion to 2-chloro-2,6-bisphenyl-1,3,5-triazine. The stirring was continued for 24 h at room temperature. The HPLC analysis showed the cyanuric chloride conversion to 92% with >96% being 2-chloro-4,6-bisphenyl-1,3,5-triazine and less than 2% of 2,4,6-trisphenyl-1,3,5-triazine. The result was confirmed by LCMS.
Part B: Preparation of 2-(2,4-dihyrdroxyphenyl)-4,6-bisphenyl-1,3,5-triazine
To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was heated to 80° C. Within 2 h, HPLC analysis indicated about 80% of 2-chloro-4,6-bisphenyl-1,3,5-triazine conversion to 2-(2,4-dihydroxyphenyl)-4,6-bisphenyl-1,3,5-triazine.
Comparative Example 61
Preparation of 2-chloro-4,6-bisphenyl-1,3,5-triazine without Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added 1.95 eq of benzene and the reaction mixture was stirred at ice bath temperature for 10 minutes. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and stirred. After about 26 h, an HPLC analysis indicated almost no cyanuric chloride conversion and no presence of 2-chloro-4,6-bisphenyl-1,3,5-triazine. The stirring was continued for an additional 24 h at room temperature. An HPLC analysis showed almost no cyanuric chloride conversion and no 2-chloro-4,6-bisphenyl-1,3,5-triazine.
Example 62
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine
Part A: Preparation of 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine Using Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added concentrated HCl (13 wt % based on cyanuric chloride). After 10 minutes, 1.9 eq of toluene was added and the reaction mixture was stirred at ice bath temperature for 30 minutes. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and stirred for 21 h. HPLC analysis indicated about 95% cyanuric chloride conversion to 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine and the isomer 2-chloro-4-(4-methylphenyl)-6-(2-methylphenyl)-1,3,5-triazine.
Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine
To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was heated to 80° C. Within 3 h, an HPLC analysis indicated 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine had converted to 2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine. HPLC analysis of the crude product showed 78% of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 11% of the isomer with probable structure of 2-(2,4-dihydroxyphenyl)-4-(4-methylphenyl)-6-(2-methylphenyl)-1,3,5-triazine.
Comparative Example 62
Preparation of 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine without Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added 1.9 eq of toluene and the reaction mixture was stirred at ice bath temperature for 10 minutes. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature. After about 2 h, an HPLC analysis indicated no reaction of cyanuric chloride. The stirring was continued for about 20 h at room temperature. HPLC analysis showed almost no reaction of cyanuric chloride and the absence of 2-chloro-4,6-bis(4-methylphenyl)-1,3,5-triazine.
Example 63
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(3 4-dimethylphenyl)-1,3,5-triazine
Part A: Preparation of 2-chloro-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine Using Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added concentrated HCl (13 wt % based on cyanuric chloride). After 30 minutes, the reaction was further cooled to about −5° C. and 1.9 eq of xylene was added. The reaction mixture was stirred at about 0° C. for 2 h, and then at room temperature for 4 h. HPLC analysis indicated >95% cyanuric chloride conversion to 82% 2-chloro-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine and 6% of its isomer.
Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(3 4-dimethylphenyl)-1,3,5-triazine
To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was heated to 80° C. Within 2 h, an HPLC analysis indicated 2-chloro-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine and its isomer had completely reacted to form 83% of 2-(2,4-dihydroxyphenyl)-4,6-bis(3,4-dimethylphenyl)-1,3,5-triazine and 6% of its isomer.
Comparative Example 63
Preparation of 2-chloro-4,6-bis(3,4-methylphenyl)-1,3,5-triazine without Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added 1.9 eq of o-xylene and the reaction mixture was stirred at ice bath temperature for 1 h. The cooling bath was removed and the reaction mixture was allowed to warm to room temperature. After about 2 h, an HPLC analysis indicated no reaction of cyanuric chloride. The stirring was continued for about 20 h at room temperature. HPLC analysis showed no significant conversion of cyanuric chloride and the absence of 2-chloro-4,6-bis(3,4-methylphenyl)-1,3,5-triazine.
Example 64
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-biphenyl)-1,3,5-triazine
Part A: Preparation of 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine Using Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added concentrated HCl (13 wt % based on cyanuric chloride). After 10 minutes, 2 eq of biphenyl was added and the reaction was stirred at ice bath temperature for 1 h. HPLC analysis indicated 88% cyanuric chloride conversion to 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine as the major product. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and stirred. HPLC analysis after 3 h at room temperature indicated about 93% cyanuric chloride to 2-chloro-4,6-bis(4-biphenyl) as the major product and confirmed by MS.
Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-biphenyl)-1,3,5-triazine
To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was heated to 85° C. for 2 h. HPLC and MS analysis indicated the formation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-biphenyl)-1,3,5-triazine.
Comparative Example 64
Preparation of 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine without Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added 2 eq of biphenyl and the reaction mixture was stirred at ice bath temperature for 1 h. HPLC analysis indicated almost no cyanuric chloride conversion and the absence of 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine. The cooling bath was removed and the reaction mixture was allowed to warm to room temperature. After about 3 h, an HPLC analysis indicated no reaction of cyanuric chloride and no formation of 2-chloro-4,6-bis(4-biphenyl)-1,3,5-triazine.
Example 65
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine
Part A: Preparation of 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine Using Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added concentrated HCl (13 wt % based on cyanuric chloride). After 10 minutes, 1.95 eq of tert-butylbenzene was added and the reaction was stirred at ice bath temperature for 10 minutes. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and stirred. After 2 h, HPLC analysis indicated 62% cyanuric chloride conversion to 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine as the major product (>78%). The reaction mixture was stirred at room temperature for an additional 24 h. HPLC analysis showed 83% cyanuric chloride conversion to 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine as the major product (>72%), with the isomer.
Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine
To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was heated to 80° C. for 2 h. HPLC analysis indicated 63% formation of 2-(2,4-dihyroxyphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine.
Comparative Example 65
Preparation of 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine without Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene at ice bath temperature was added 1.95 eq of tert-butylbenzene. The reaction mixture was stirred at ice bath temperature for 10 minutes. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and stirred. After about 2 h, an HPLC analysis indicated no reaction of cyanuric chloride and no 2-chloro-4,6-(4-tert-butylphenyl)-1,3,5-triazine formation. The stirring was continued for about 24 h at room temperature. HPLC analysis showed no 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine formation.
Example 66
Preparation of 2-(2,4-dihydroxy-5-hexylphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine
Part A: Preparation of 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine Using Concentrated HCl
2-Chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine was prepared essentially following the procedure described in example 67.
Part B: Preparation of 2-(2,4-dihydroxy-5-hexylphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine
To the above reaction mixture was added 1.1 eq of 4-hexylresorcinol and the mixture was heated to 80° C. for 3 h. HPLC analysis indicated conversion of 2-chloro-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine to 2-(2,4-dihydroxy-5-hexylphenyl)-4,6-bis(4-tert-butylphenyl)-1,3,5-triazine as the major product.
Example 67
Preparation of 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
Part A: Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
2-Chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine was prepared by allowing to react 1 eq of cyanuric chloride with 1.9 eq of m-xylene in the presence of 3 eq of aluminum chloride and concentrated HCl in chlorobenzene as discussed above.
Part B: Preparation of 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
To the above reaction mixture was added 1.1 eq of resorcinol monooctyl ether and the mixture was stirred at room temperature for about 20 h. TLC analysis indicated formation of 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine as the major product by a direct comparison with a commercial sample of 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 68
Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
Part A: Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; Simultaneous Addition of Cyanuric Chloride and m-xylene to Reaction Facilitator Prepared from Aluminum Chloride and Concentrated HCl
To a stirring mixture of 3 eq of aluminum chloride in chlorobenzene at 0° C. to 5° C. was added concentrated HCl (6 wt % based on aluminum chloride), and the reaction mixture was stirred for 10 minutes to form the reaction facilitator. To the mixture was added a solution of 1 eq of cyanuric chloride and 1.9 eq of m-xylene in chlorobenzene at 0° C. to 5° C. and the reaction was stirred for 10 minutes. HPLC analysis indicated 95% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (99%). The reaction mixture was allowed to stir at 0° C. to 5° C. for 2 h. HPLC analysis showed 99% cyanuric chloride conversion to 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine (98%).
Part B: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
To the above reaction mixture was added 1.1 eq of resorcinol and the mixture was heated to 80° C. for 2 h. HPLC analysis indicated 95% of 2-(2,4-dihyroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 69
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine in Benzene as Solvent and Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in benzene at 7° C. was added concentrated HCl (13% wt based on cyanuric chloride), and the mixture was stirred for 10 minutes. To the reaction mixture was added 1.9 eq of m-xylene and the reaction mixture was stirred at 0° C. for 30-35 minutes. The cooling bath was removed, the reaction mixture was allowed to warm to room temperature, and stirred for 3 h. HPLC analysis indicated >97% cyanuric chloride conversion to 2-chloro-4,6-(2,4-dimethylphenyl)-1,3,5-triazine (85%).
Example 70
Preparation of 2-(2,4-dihydroxy-6-methylphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
Part A: Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Complex with Reaction Facilitator Prepared from Aluminum Chloride and Concentrated HCl
To a stirring mixture of 1 eq of isolated 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 3 eq of aluminum chloride in o-dichlorobenzene was added concentrated HCl (5.9 wt % based on aluminum chloride). After stirring for about 5-6 h at room temperature, the reaction turned orange-red, indicative of a new complex formed between the reaction facilitator, consisting of aluminum chloride and concentrated HCl, and 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Part B: Preparation of 2-(2.4-dihydroxy-6-methylphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
The above complex mixture was heated to about 60° C. To the mixture was added 1 eq of orcinol (5-methylresorcinol), and the reaction mixture was heated to 80° C. to 85° C. for 8 h. HPLC analysis indicated almost complete conversion of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine leading to the formation of 2-(2,4-dihyroxy-6-methylphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Comparative Example 70
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Complex with Aluminum Chloride without Concentrated HCl
A mixture of 1 eq of isolated 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 3 eq of aluminum chloride in o-dichlorobenzene was stirred at room temperature for about 5-6 h. The reaction mixture turned slightly yellow and was not orange-red as in the preceding example, indicative of a lack of the new complex formation from 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
Example 71
Preparation of Reaction Facilitator from Aluminum Chloride and Concentrated HCl
To a stirring mixture of 3 eq of aluminum chloride in o-dichlorobenzene was added concentrated HCl (6 wt % based on aluminum chloride). The reaction mixture was stirred at room temperature. The formation of a new off-white mixture of the reaction facilitator was observed, which did not change its color even after stirring at room temperature for 2 h.
Example 72
Preparation of 2,4,6-trichloro-1,3,5-triazine (Cyanuric Chloride) Complex with Reaction Facilitator Prepared from Aluminum Chloride and Concentrated HCl
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene was added concentrated HCl (13 wt % based on cyanuric chloride). The reaction mixture turned brownish-red after 30 minutes of stirring at room temperature. The reaction became dark brown after an additional 1 h of stirring at room temperature. The color of the reaction mixture indicated the formation of a new complex between cyanuric chloride and the reaction facilitator prepared from aluminum chloride and concentrated HCl.
Comparative Example 72
Preparation of 2,4,6-trichloro-1,3,5-triazine (Cyanuric Chloride) Complex with Reaction Facilitator Prepared from Aluminum Chloride without Concentrated HCl
A mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in o-dichlorobenzene was stirred at room temperature for 3 h. No change in color from original off-white was observed, indicating lack of a similar complex formation of cyanuric chloride as in the preceding example, where cyanuric chloride was treated with the reaction facilitator consisting of aluminum chloride and concentrated HCl.
Example 73
Preparation of 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Using Aliquat-336
To a stirring mixture of 1 eq of cyanuric chloride and 3 eq of aluminum chloride in benzene at about 0° C. was added Aliquat-336 (tricaprylylmethylammonium chloride) (50 wt % based on aluminum chloride). A reaction with aluminum chloride was observed with temperature increase. The reaction mixture was stirred at room temperature for 30 minutes, leading to the formation of a clear orange-red solution. To the resulting complex of cyanuric chloride with reaction facilitator was added 1.9 eq of m-xylene and the reaction mixture was stirred at room temperature for 1 h. HPLC analysis indicated almost 90% cyanuric chloride conversion to 2-chloro-4,6-(2,4-dimethylphenyl)-1,3,5-triazine as the major product and 2,4,6-tris(2,4-dimethylphenyl)-1,3,5-triazine as the minor product, formed in a ratio of 3:1.
The invention described and claimed herein is not to be limited in scope by the specific embodiments herein disclosed, since these embodiments are intended as illustrations of several aspects of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.
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It has been now surprisingly discovered after extensive research that 2-halo-4,6-bisaryl-1,3,5-triazine can be prepared with unprecedented selectivity, efficiency, mild conditions, and in high yield by the reaction of cyanuric halide with aromatics in the presence of at least one Lewis acid and at least one reaction promoter. This reaction is also unprecedently general as a variety of aromatics can be used to produce a wide selection of 2-halo-4,6-bisaryl-1,3,5-triazines. The novel approach includes the use of the reaction promoters in combination with at least one Lewis acid under certain reaction conditions to promote the formation of 2-halo-4,6-bisaryl-1,3,5-triazine compounds from cyanuric halide. Preferably, the Lewis acids and reaction promoters are combined to form a complex. 2-Halo-4,6-bisaryl-1,3,5-triazines are key intermediates for making 2-(2-oxyaryl)-4,6-bisaryl-1,3,5-triazine class of UV absorbers.
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BACKGROUND OF THE INVENTION
This invention is directed to high speed pick-up heads of the type disclosed in commonly assigned U.S. Pat. Nos. 3,512,206 and 3,545,181 in the name of Bernard W. Young issued respectively on May 19, 1970 and Dec. 8, 1970 and respectively titled AIR FLOW SURFACE CLEANING APPARATUS and AIR CLEANING APPARATUS.
The latter patents disclose a vehicle which carries a pick-up head, a centrifugal separator, a hopper, and assignee's Regenerative® air circulating system. Air generated by a turbine is directed through a blast orifice of the pick-up head, admixes with and propels the debris to a suction orifice of the pick-up head after which the debris is centrifugally separated and discharged in the hopper, and the air returns to the blast orifice. In this manner debris on roads, roadways, packing lots or the like can be rapidly and efficiently removed. However, while the apparatus of the latter patents represented state-of-the-art at the time of patenting and continues to do so to date, continued experimentation, research and development has resulted in yet greater efficiency and higher speeds of both debris removal and vehicle travel. Furthermore, the art of road sweepers has advanced considerably since the early 1970's and has become considerably more sophisticated and specialized. It is particularly because of these reasons that the present invention has been developed.
SUMMARY OF THE INVENTION
The present invention is directed to a high speed pick-up head which is of an extremely simple and straightforward construction utilizing minimal components; aerodynamic shape, construction and orientation of air pressure and air suction chambers, selective blast orifice adjustment, and minimum pick-up head to ground clearance to maximize blast air velocity which collectively assure that debris, particularly small high-mass debris, such as grains of sand, pebbles, pea-gravel or the like can be cleaned from surfaces, specifically and particularly airport runways.
In accordance with the foregoing, the novel high-speed pickup head of this invention includes an air pressure chamber and an air suction chamber respectively associated with a blast orifice and a suction orifice, the air pressure chamber and air suction chamber being positioned in side-by-side relationship generally normal to the direction of vehicle/pick-up head travel, the chambers having opposite first and second ends, each chamber defining an elongated volume corresponding in length generally to the orifice associated therewith with each chamber volume decreasing in cross-sectional area toward a closed end of the associated chamber, and the air pressure chamber having an air inlet at an end thereof opposite to an air outlet of the suction chamber.
The novel high speed pick-up head of this invention further includes means for varying the shape and/or size of the blast orifice to maintain generally uniform high speed velocity across the length thereof whereby maximum debris entrainment will occur for virtually any cfm (cubic feet per minute) of air flow created by an associated blower or turbine, and the blast orifice adjustment preferably creates a blast orifice of a generally diverging configuration in a direction away from the air pressure chamber air inlet toward the opposite closed end thereof.
In further accordance with this invention the high speed pick-up head includes a relatively flat top plate which is supported by side skid plate assemblies at a minimum distance above a surface which is to be cleaned of debris whereby maximum air movement is created between the blast orifice and the suction orifice thereby creating high speed air propulsion which blasts or blows sand, small heavy or dense pebbles or stones, chips or the like from a surface, such as an airport runway, or small stones or chips associated with so-called chip-seal programs of roads enabling corresponding high speed vehicle movement during debris removal and consequent increased efficiency.
The head speed pick-up head of the invention further includes a drain opening in a top plate or wall of the overall pick-up head assembly for cleaning debris therefrom by a simple flushing operation.
With the above and other objects in view that will hereinafter appear, the nature of the invention will be more clearly understood by reference to the following detailed description, the appended claims and the several views illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded perspective view of the high speed pick-up head of this invention, and illustrates a suction head assembly and its associated tapering suction chamber, a pressure chamber assembly and its associated tapering air pressure chamber, a generally horizontal plate of the pressure chamber, and suction and blast orifices assemblies thereof.
FIG. 2 is a top plan view of the high speed pick-up head, and ilustrates the manner in which the air pressure chamber and suction chamber taper from maximum to minimum cross-sectional area in opposite directions with the respective pressure inlet and suction outlet thereof being remote from each other and at the larger volumed ends of the associated chambers.
FIG. 3 is a bottom plan view of the high speed pick-up head and more clearly illustrates the blast orifices on the right, the suction orifice on the left, and a relatively flat plate therebetween.
FIG. 4 is an enlarged cross-sectional view taken generally along line 4--4 of FIG. 2, and illustrates the manner in which high pressure air is delivered to the blast orifice, travels from right-to-left along the surface to be cleaned, and is drawn with entrained debris into the suction orifice.
FIG. 5 is a diagrammatic cross-sectional view taken generally along line 5--5 of FIG. 2, and illustrates the smaller end of the elongated blast orifice formed by a flexible blast curtain which is forced open by the air pressure adjacent the air pressure inlet of the air pressure chamber.
FIG. 6 is a diagrammatic cross-sectional view taken generally along line 6--6 of FIG. 2, and illustrates the larger size of the blast orifice a the end of the pressure chamber remote from the air pressure inlet thereof.
FIG. 7 is a fragmentary cross-sectional view taken generally along line 7--7 of FIG. 5 with parts removed for clarity, and illustrates the manner in which the blast orifice opens in a diverging direction away from the air inlet of the air pressure chamber.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A novel high-speed pick-up head of this invention is generally designated by the reference numeral 10 and includes an air pressure chamber assembly 11 and a suction head assembly or air suction assembly 12.
The air pressure chamber assembly 11 includes a relatively rigid rectangular metallic plate 13 having a forward longitudinal edge 14, a rear bent edge or bend 15, opposite transverse edges (unnumbered), an upper surface 16 (FIGS. 1 and 2) and a lower surface 17 (FIGS. 3 through 7). The forward edge 14 includes a plurality of spaced elongated slots 18 for securing the suction head assembly 12 thereto, as will be more apparent hereinafter. Upstanding side plates 20, 21 (FIG. 1) having vertical slots 22 are welded to the transverse or side edges of the plate 13.
The plate 13 has bolted thereto four identical up-stop tabs or L-shaped brackets 23, and between and connected to associated pairs of the up-stop tabs 23 are up-stop tower assemblies 24, each having an uppermost generally horizontal up-stop plate 25, and opposite generally parallel upstanding flanges 26 of which at least one flange has a plurality of openings 27.
The plate 13 is reciprocally, suspendingly supported beneath a vehicle (not shown) in the manner fully disclosed in the latter-identified patents, such that the forward edge 14 leads the rear edge 15 in the direction of vehicle travel which is generally designated by the headed arrow DT in FIG. 1. In the operative or running position of the high speed pick-up head 10 (FIGS. 4 through 6) the plate 13 is in intimate spaced relationship from the surface S which is being cleaned of debris D. In this position the high speed pick-up head 10 is resiliently suspended from the vehicle (not shown) by conventional flexible supports in the form of front springs 30 (FIG. 1) and rear springs 31, each connected by a chain link 32 to the holes 27 in the flanges 26 of the up-stop tower assemblies 24. Ends of the springs 30, 31 remote from the chain links 32 have threaded ends 33 which are received in apertures (not shown) or brackets (also not shown) welded to the vehicle and secured thereto by nuts (not shown).
The high speed pick-up head 10 is moved between raised and lowered positions by a pair of identical lift cylinders 35, each having a rod 36 connected to a clevis or bracket 37 which is in turn connected to a pin 38 to an associated one of the holes 27 of the upstanding flanges 26 of the up-stop tower assemblies 24. Each cylinder 35 is also connected by a bifurcated end 40 and a pin 41 to an aperture 42 of a downwardly directed bracket 43 of an up-stop assembly 45. Each up-stop assembly 45 includes a channel member 46 having a plurality of openings 47 in opposite side walls (unnumbered) thereof for connection to the frame of the vehicle. The channel member 46 is welded to a leg 48 having a lower foot 51 positioned at a specific distance below the vehicle from and above the plates 25 of the upstop tower assemblies 24 when the rods 36 are projected out of their associated cylinders 35 in the running or lowered position of the high speed pick-up head 10 (FIGS. 4 through 6). However, when the rods 36 are drawn into the cylinders 35, the pick-up head 10 is lifted until the feet 51 bottom against the plates 25 of the up-stop tower assemblies 24 to thereby hold the pick-up head 10 rigidly against the up-stop assemblies 45 for high speed vehicle travel in the raised or inoperative position of the pick-up head 10.
Conventional skid plate assemblies, plates or skids 52 are connected by a plurality of nuts and bolts 53 to the slots 22 of the side plates 20, 21 to hold the plate 13 of the pick-up head 10 a predetermined distance above the surface S, as is most readily apparent from FIG. 4 of the drawings, and define therewith a working chamber or pick-up head chamber C.
Reference is made particularly to FIGS. 1, 2 and 4 of the drawings in which the suction head assembly 12 is shown, and includes an elongated air suction chamber 60 having an air outlet or air suction outlet 61 of a generally circular configuration to which is conventionally attached a suction hose 62 which is in turn connected to the centrifugal separation chamber (not shown) of the vehicle, as in the latter-identified patents. The suction chamber 60 includes a first closed end portion 63 and a relatively larger second end portion 64 defining therebetween and therewith a generally elongated volume which decreases progressively in cross-sectional area from the largest volume at the end portion 64 and the suction outlet 61 toward the smallest volume at the closed end or end portion 63. A forward side wall 65 (FIG. 4) and a rearmost side wall 66 converge downwardly, as is best shown in FIG. 4. The rearmost side wall 66 merges with an angularly bent plate formed of a plurality of plate portions 67, 68, 70 (FIG. 4) with the latter having an upwardly directed reinforcing flange 71. The plate portions 67, 68 and 70 and the flange 71 extend the entire length of the suction chamber 60, generally corresponding to the length of the plate 13. Furthermore, the plate portion 70 has a plurality of openings 72 spaced from each other the same distance as the distance between the slots 18 so that appropriate nuts and bolts 73 (FIG. 4) can removably connect the suction head assembly 12 to the upper surface 16 of the plate 13 along the forward edge 14. The juncture between the plate portions 68, 70 (FIG. 4) is generally in alignment with the forward or leading edge 14 of the plate 13 and collectively define the rearmost edge (generally at 14) of an air suction or suction orifice 80 which extends the length of the underside of the suction chamber 60 generally between the side plates 20, 21. The size of the suction 80 can be varied in a limited fashion in the transverse direction or direction of vehicle travel DT by simply loosening the nuts and bolts 73 and shifting the entire suction head assembly 12 to the right, as viewed in FIG. 4, which will move the junction between the plates 68, 70 to the right of the edge 14 of the underlying plate 13. In this fashion the edge 14 effectively restricts the transverse size of the suction orifice 80. The opposite side of the suction orifice 80 is defined by a curtain 81 of a pair of curtains 81, 82 which likewise run the length of the suction head assembly 12 and are part of a suction head curtain assembly 84 (FIG. 1).
The suction head curtain assembly 84 includes an elongated bar 85 of a generally shallow inverted U-shaped configuration having a plurality of holes 86 which are aligned with holes 87 in a forward plate or flange 90 of the suction head assembly 60. Suitable nuts and bolts can thereby secure the bar 85 to the underside of the flange 90, as is most readily apparent from FIG. 4. The curtain 81 is connected by nuts and bolts to one depending leg (unnumbered) of the bar 85 while similar nuts and bolts connect the curtain 82 to the remaining depending leg or flange of the bar 85, again as is most evident in FIG. 4. As the pick-up head 10 moves in the direction DT in FIG. 4, the lower ends (unnumbered) of the curtains 81, 82 deflect or curve, and this curvature of the curtain 81 provides a relatively smooth transition for air flow into the orifice 80 along the entire length thereof (FIG. 3).
The pick-up head 10 is preferably articulately connected to the vehicle through a pair of drag links 95 having opposite ends conventionally pivotally connected to brackets 96 fixed to the forwardmost wall 65 of the suction chamber 60 and apertured extension links 97 (FIG. 1) having upper ends welded or otherwise connected to the vehicle frame. The articulated connections permit the vehicle to pull the pick-up head 10 in the direction DT (See FIG. 4) without placing excessive strain upon the lift cylinders 35 or the springs 30, 31.
The pressure chamber assembly 11 is similar in construction to the suction chamber assembly or suction head assembly 12 and includes a pressure chamber 100 which is in generally sid-by-side relationship to the suction chamber 60, as is most readily apparent from FIG. 2 of the drawings. The pressure chamber 100 includes a relatively large volume first end portion 101 adjacent a high pressure air inlet 102 and a second low volume and closed end portion 103 (FIGS. 1 and 2). An upwardly bent forwardmost wall portion 104 of the plate 13 and a rearmost wall 105 of the pressure chamber 100 taper convergingly downwardly and with an upper wall 106 (FIG. 2) taper generally from the end portion 101 toward the end portion 103 in a progressively decreasing cross-sectional area of chamber volume. The plates 20 and 21 close and are also welded to the end portions 103, 101 of the pressure chamber 100, as is readily apparent from FIG. 1.
The high pressure air inlet 102 is preferably part of a removable pressure lid assembly 110 (FIGS. 1, 2 and 4) which includes a generally truncated roof-like top wall 111 merging at opposite ends in two upstanding flanges 112, 113 and at opposite sides in opposing flanges 114, 115 (FIG. 4). At the second end portion 101 the pressure chamber 100 includes a pair of inverted L-shaped keepers 122 (FIGS. 1 and 2), and opposite horizontal flange 123 (FIG. 1), and a pair of generally parallel oppositely directed lateral flanges 124, 125 (FIGS. 1 and 4). A conventional keeper or catch 126 is connected to the side plate 20. The removable pressure lid assembly 110 is mounted atop the end portion 101 of the pressure chamber 100 by simply sliding the same from right-to-left in FIG. 1 until the flange 112 seats beneath the keepers 122 (FIG. 2). The catch 126 is then simply engaged with the flange 113 to lock the pressure lid assembly 110 upon the inlet end portion 101 of the high pressure chamber 100.
As is best illustrated in FIGS. 4 and 7, the rearmost wall 105 is bent at its lowermost longitudinal edge (unnumbered) into a horizontal plate 130 (FIGS. 4 and 7) having an upwardly directed reinforcing flange 131 (FIG. 7). The plate 130 also includes a plurality of elongated slots 132 to which a blast orifice assembly 135 (FIG. 1) can be adjustably connected by a series of nuts and bolts 133 to permit the overall blast orifice assembly 135 to be shifted forwardly or rearwardly, either perfectly normal to or at an angle relative to the direction of travel DT for a purpose and function to be described more fully hereinafter.
The blast orifice assembly 135 includes a stepped bar 140 having a horizontal portion 141 and an angled portion 142, both of which are reinforced by flanges (unnumbered in FIG. 4) generally normal thereto. The horizontal portion 141 of the bar 140 has a plurality of openings 143 (FIG. 1) spaced along the length thereof corresponding to the slots 132, and it is through these openings and slots that the nuts and bolts 133 unite the bar 140 to the plate 130 of the pressure chamber 100. The bar 140 runs the entire length of the pressure chamber 100 and carries at its underside two flexible curtains 144, 145 whose lower end portions (unnumbered) are deflected as best illustrated in FIG. 4 during the motion of the pick-up head 10 in the direction DT.
The portion 142 of the bar 140 of the blast orifice assembly 135 is disposed at an angle to the horizontal or surface S and secured thereto by a clamping bar 146 (FIG. 1) and a plurality of bolts (unnumbered) spaced therealong is a flexible blast orifice curtain 150 which extends the length of the pressure chamber 100 and defines an elongated blast orifice or air outlet orifice 160 which similarly extends the length of the pressure chamber 100. Reference is particularly made to FIG. 7 which illustrates the blast orifice curtain 150, as viewed from above, with the clamping bar 146 and the nuts associated therewith removed for purposes of clarity. The blast orifice curtain 150 includes a forwardmost longitudinal edge 151 and an opposite rearmost parallel edge 152. It is to be particularly noted from the upper portion of FIG. 6 that the forwardmost edge 151 of the air blast curtain 150 sets off with the bent edge 15 a portion of the blast orifice 160 which converges from top to bottom in FIG. 7 or converges in a direction toward the pressure inlet end portion 101 and slightly underlyingly overlaps the bent edge 15 at the bottom end portion of FIG. 7. This angular relationship of the edge 151 of the blast orifice assembly 135, as is readily apparent from FIG. 7, noting that the bolt 133 is at the left-hand end of the lowermost slot 132 and is at the right-hand end of the uppermost slot 132. The purpose for the progressive diverging of the blast orifice 160 in a direction toward the suction side or away from the pressure side or pressure inlet 102 is to assure that generally constant air flow is created along not only the length of the pressure chamber 100 but through the blast orifice 160 over its entire length so that the air flow across and transverse to the length of the plate 13 along the surface 17 is of a uniform velocity assuring that all debris D will be "blasted" by the air flow toward and into the suction orifice 80 of the suction chamber 60. As is most apparent from FIGS. 4 and 5, the high pressure air being introduced into the high pressure inlet portion 101 of maximum crosssectional area is directed both downwardly, and due to the smooth tapered transition of the air pressure chamber 100, in a direction from the large cross-sectional area air inlet portion 101 toward the opposite smallest cross-sectional area closed end portion 103. The high pressure air at the air inlet portion 101 directly impinging upon the upper surface of the blast curtain 105 deflects the same away from the edge 15 essentially "opening" the blast orifice 160 (FIG. 5) at the high pressure end portion 101 of the pressure chamber 100. At the same time the air is forced along the air pressure chamber 100 toward the closed end portion 103, and at the latter end portion the blast orifice 160 is already "open" (FIG. 6 and upper end of FIG. 7), thus offering less resistance of high pressure air flow toward the open portion of the blast orifice 160 (upper half of blast orifice 160 of FIG. 7). Accordingly, by selectively orienting the edge 151 of the blast curtain 150 relative to the edge 15, the velocity of the air exiting the orifice 160 transversely thereto and transversely to the plate 13 can be regulated and, most importantly, can be maintained at a generally constant flow rate across the entirety of the plate 13. Accordingly, due to the uniform velocity of the air flow between the side plates 20, 21 in the direction DT, any debris D beneath the plate 13 between the side plates 20, 21 will be subject to substantially uniformed air velocity and, thus, "blasted" from right-to-left in FIGS. 4 through 6 across the working chamber C toward and into the suction opening 80 for centrifugal separation and eventual continuous recirculation of the air back through the air pressure inlet 102. Thus, the combination of the progressively decreasing cross-sectional area/tapering of the air pressure chamber 100 from the pressure inlet side 101 toward the closed end portion 103 together with the divering nature of the blast orifice 160 in the same direction (from the side 20 toward the side 21 or from the high pressure inlet 101 toward the closed end portion 103) assures uniform high velocity air flow virtually in a uniform transverse curtain or parallel streams, as indicated by the headed arrows shown in FIG. 3 in somewhat parallel relationship, along the surface 17 of the plate 13.
Furthermore, it is readily apparent that though the air velocity exiting the blast orifice 160 is uniform along its length, without assurance of corresponding withdrawal of air through the suction orifice 80, the flow path across the surface 17 will be disturbed. Accordingly, to assure that such counter-balancing of air exiting the blast orifice 160 and entering the suction orifice 80, the tapering of the suction chamber 60 is the reverse of that of the pressure chamber 100, as is also readily apparent in FIGS. 1, 2 and 3. Thus, maximum and uniform withdrawal of air and entrained debris is assured as pressurized air circulation continues. Furthermore, as noted heretofore, the nuts and bolts 73 of the suction head assembly 12 can be appropriately manipulated to vary the size and shape of the suction orifice 80 as defined between the edge 14 of the plate 13 and the curtain 81. Obviously, this change in size can be uniform by maintaining the edge 14 generally parallel to the curtain 81 or cocked thereto.
Obviously, the ede 151 of the blast orifice curtain 150 need not be "cocked", as shown in FIG. 7, but can be uniformly spaced from and parallel to the edge 15. Furthermore, the edge 151 need not be spaced partially or entirely from the edge 15 but might, for example, be tapered divergingly the entire distance from bottom to top (as viewed in FIG. 7) so that the curtain 150 would be deflected to a minimal degree at the high pressure inlet portion 101. Thus, rather than the cross-over of the blast orifice 160 shown in FIG. 7 with the edge 15 essentially underlying half the edge 15 and being spaced from the other half, the blast orifice 160 could be virtually a completely opened triangular orifice converging completely from top to bottom, as viewed in FIG. 7. If, of course, the edges 151 and 15 were spaced completely from each other and in parallel relationship to each other, the orifice 160, instead of being generally triangular, would be generally polygonal or rectangular. Obviously, the purpose of the variation and the orientation of the blast orifice curtain 150 is to assure that the air exiting along the length of the blast orifice 160 is of both maximum and uniformed velocity across the surface 17 from end to end (between side walls 20 and 21) to assure maximized motion of the debris, particularly in the case of gravel, sand or the like on runways of airports which heretofore has proved a most difficult problem for "conventional" pick-up heads at high speeds. It is for this reason also that the surface 17 of the plate 13 is spaced extremely close (approximately 2 inches) from the surface S and is virtually perfectly horizontal and flat so that the air flow/pressure/velocity is maximized to "blast" the debris D along the surface S toward and into the suction opening 80 across the working chamber C.
It will be readily apparent from the drawings that the construction of the pick-up head thus far described sets-off a generally upwardly opening volume (unnumbered) defined by the side walls 20, 21 (FIG. 1) and the area between the pressure chamber assembly 11 and the suction head assembly 12 or, stated otherwise, the area above the plate 13. During continuous high-speed vehicle travel and operation, debris D will settle and accumulate upon the plate 13. Means 170 is provided in the plate 13 in the form of a circular hole which is normally closed by a flexible rectangular curtain or flap 171 fixed to the plate 13 by a plate and bolts collectively identified by the reference numeral 172 in FIG. 1. When the pick-up head is in operation, the inherent flexibility of the drain curtain 171 is sufficient to resist upward deflection and in actual practice has been found to be an excellent over-pressure release should, for example, the suction orifice 80 become clogged during operation. In such cases limited air can escape through the hole 170 as the drain curtain 171 is deflected upwardly, as indicated by the unnumbered headed arrow associated therewith in FIG. 4. However, while this release of over-pressure in the pick-up head chamber (C, FIG. 4) beneath the plate 13 is highly desirable, it is not totally necessary, and the main purpose for the hole 170 and the curtain 171 is simply to permit flushing of debris from the upper surface 16 of the plate 13 by directing a stream of water thereupon with, of course, the free edge (unnumbered) of the curtain 171 held up or underfolded, as indicated in phantom outline in FIG. 4. In either case a stream of water from a hose directed upon the surface 16 will flush debris therefrom into and through the hole 170 and into the pick-up head chamber C.
Although a preferred embodiment of the invention has been specifically illustrated and described herein, it is to be understood that minor variations may be made in the apparatus without departing from the spirit and scope of the invention, as defined in the appended claims.
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A high-speed pick-up head includes an air pressure chamber and an air suction chamber respectively associated with an elongated blast orifice and a suction orifice. The chambers are arranged in side-by-side relationship generally normal to the direction of vehicle/pick-up head travel and have opposite first and second ends. Each chamber defines an elongated volume corresponding in length generally to the orifice associated therewith with each volume decreasing in cross-sectional area toward its closed end. Respective air inlets and air outlets of the pressure and suction chambers are opposite each other and the blast orifice can be changed in size and/or shape, preferably diverging in a direction away from the pressure chamber air inlet to maintain maximum air velocity/flow which blasts or blows sand or similar dense debris from airport runways for subsequent removal/separation at extremely high efficiencies.
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BACKGROUND OF THE INVENTION
The present invention relates generally to subterranean well systems having multiple tubular strings installed therein and, in one embodiment described herein, more particularly provides a dual string completion system utilizing an improved wye block.
It is well known in the art to interconnect an upper tubular string to multiple lower tubular strings in a subterranean well utilizing a device known as a wye block. The wye block typically has an upper threaded connection for attachment to the upper tubular string, and multiple lower threaded connections for attachment to the multiple lower tubular strings. In this manner, fluid communication is established between the upper tubular string and each of the multiple lower tubular strings so that, for example, fluids from different formations or zones intersected by the well and produced through corresponding ones of the multiple lower tubular strings may be flowed to the earth's surface via the upper tubular string.
The wye block derives its name from the fact that it has a generally Y-shaped body or housing when it is configured to interconnect a single upper tubular string to two lower tubular strings. In a more general sense, and as used herein, however, the term “wye block” includes configurations in which two or more tubular strings are interconnected to another tubular string by the wye block body or housing. Additionally, the term “wye block” is not restricted to configurations in which a single tubular string extends in an upward direction therefrom and multiple tubular strings extend in a downward direction therefrom, although this may be the most commonly used configuration.
As stated above, the typical wye block provides fluid communication between the interconnected tubular strings via their attachment to the wye block body or housing. However, providing convenient access between each of the tubular strings is a far more difficult proposition. For example, if it is desired to convey a wireline tool or a coiled tubing string from the earth's surface into a certain one of the lower tubular strings, a device or mechanism should be provided in the wye block to direct the wireline tool or coiled tubing string from the upper tubular string, into the desired one of the lower tubular strings, and not into any other of the lower tubular strings. In addition, the device or mechanism should be capable of being repositioned when it is desired to permit access to another selected one of the lower tubular strings. Furthermore, the device or mechanism should not impede flow through the wye block during fluid production from the well, and should be reliable in operation, convenient to operate, and not subject to damage and deterioration during wellbore operations.
One proposed method of accomplishing these objectives is to construct the wye block with a diverter mechanism therein. The diverter mechanism may be a type of hinged flapper which, when positioned to one side in the wye block, will divert the tool or coiled tubing string toward a selected one of two lower tubular strings and, when positioned to the other side in the wye block, will divert the tool or coiled tubing string to the other lower tubular string. Openings may be provided in the flapper to permit fluid flow therethrough.
Unfortunately, such diverter mechanisms have several shortcomings. For example, the hinged flapper is subject to erosion and other deterioration, due to substantially constant fluid flow therethrough. Debris may accumulate about the diverter mechanism, preventing its subsequent operation. The openings formed through the flapper are typically not equivalent to a full bore opening. Only two lower tubular strings may be selected among by the diverter mechanism. In addition, a positive indication at the earth's surface is usually not available for determining whether the diverter mechanism has actually selected the desired lower tubular string for access thereto.
In view of the foregoing, it will be appreciated that a need exists for an improved wye block and improved methods of servicing wells in which multiple tubular strings are interconnected.
SUMMARY OF THE INVENTION
In carrying out the principles of the present invention, in accordance with an embodiment thereof, an improved wye block is provided in which a guide structure thereof is automatically aligned with a selected one of multiple tubular string connections. In a described method of servicing a subterranean well, the guide structure is separately conveyed as a part of an access control assembly into a housing assembly of the wye block after the wye block has been installed in the well interconnecting multiple tubular strings.
In one aspect of the present invention, the wye block housing assembly is installed in the well interconnecting multiple tubular strings. An access control assembly is then separately conveyed into the housing assembly when it is desired to access one of the tubular strings attached to the wye block housing assembly. The access control assembly includes a guide surface which is automatically aligned with a selected one of the tubular strings when the access control assembly is installed in the housing assembly.
In another aspect of the present invention, the access control assembly includes at least first and second portions. By securing the first portion relative to the second portion before the access control assembly is installed in the wye block housing assembly, the selected one of the tubular strings is determined before the access control assembly is conveyed into the well.
In still another aspect of the present invention, the access control assembly first portion engages an orienting device of the wye block housing assembly when the access control assembly is installed in the housing assembly. The orienting device may be a generally helically-shaped orienting profile, so that the access control assembly second portion is rotationally aligned with the selected one of the tubular strings when the access control assembly is installed in the housing assembly.
These and other features, advantages, benefits and objects of the present invention will become apparent to one of ordinary skill in the art upon careful consideration of the detailed description of representative embodiments of the invention hereinbelow and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematicized view of a method of servicing a subterranean well embodying principles of the present invention;
FIGS. 2A-2C are quarter-sectional views of successive axial sections of an access control assembly embodying principles of the present invention; and
FIGS. 3A-3E are cross-sectional views of successive axial sections of an access control apparatus embodying principles of the present invention, a housing assembly thereof having the access control assembly of FIGS. 2A-2C installed therein.
DETAILED DESCRIPTION
Representatively illustrated in FIG. 1 is a method 10 of servicing a subterranean well, which method embodies principles of the present invention. In the following description of the method 10 and other apparatus and methods described herein, directional terms, such as “above”, “below”, “upper”, “lower”, etc., are used for convenience in referring to the accompanying drawings. Additionally, it is to be understood that the various embodiments of the present invention described herein may be utilized in various orientations, such as inclined, inverted, horizontal, vertical, etc., without departing from the principles of the present invention.
In the method 10 , a wye block or access control apparatus 12 is installed in a well interconnecting an upper production tubing string 14 to two lower production tubing strings 16 , 18 . The lower string 16 extends downwardly into a lower main or parent wellbore 20 , wherein it is sealingly engaged within a tubular member 22 utilizing a packer 24 . The tubular member 22 is attached to a hollow whipstock 26 sealingly engaged in the lower parent wellbore 20 via another packer 28 .
The lower string 18 extends downwardly from the wye block 12 and laterally outwardly through a window 30 formed through casing 32 and cement 34 lining the parent wellbore. The lower string 18 extends into a branch or lateral wellbore 36 drilled outwardly from the window 30 . A packer 38 provides sealing engagement between the lower string 18 and a liner 40 cemented within the lateral wellbore 36 .
It will be readily appreciated that fluid produced from the lateral wellbore 36 may be flowed via the lower string 18 to the wye block 12 , and that fluid from the lower parent wellbore 20 may be flowed via the lower string 16 to the wye block. From the wye block 12 , the commingled fluids may be flowed through the upper string 14 to the earth's surface. Of course, these directions of fluid flow may be reversed if the strings 14 , 16 , 18 are utilized for injection rather than production of fluids.
It is to be clearly understood, however, that the method 10 is merely illustrative of the wide variety of methods of servicing a well and configurations of tubular strings and equipment therein which may embody principles of the present invention. For example, there may be more than two tubular strings attached to one end of the wye block 12 , it is not necessary for one of the strings to extend into a lateral wellbore, it is not necessary for one of the strings to extend through a hollow whipstock, it is not necessary for the wye block to be configured or oriented as shown in FIG. 1, etc. Thus, it will be readily appreciated that other methods may be practiced, and many modifications may be made to the depicted method 10 , without departing from the principles of the present invention.
In one unique aspect of the method 10 , an access control assembly is conveyed into the wye block 12 after the wye block has been installed in the well interconnecting the tubular strings 14 , 16 , 18 and when it is desired to provide access to a selected one of the lower strings. In this manner, the access control assembly is not present in the wye block 12 when access to a particular one of the lower strings 16 , 18 is not required. Thus, the access control assembly is not left in the wye block 12 to deteriorate, become fouled with debris, and block or restrict fluid flow through the wye block.
In another unique aspect of the method 10 , the access control assembly is automatically aligned so that it permits access to the selected one of the lower strings 16 , 18 when it is installed in the wye block 12 . In this manner, it is not necessary to engage the access control assembly with a wireline shifting tool or other tool downhole in order to align the access control assembly with the selected string. Instead, the access control assembly is appropriately configured at the earth's surface so that, when it is installed within the wye block 12 , a guide structure of the access control assembly is automatically oriented to permit access to the selected string.
Referring additionally now to FIGS. 2A-2C, an access control assembly 50 embodying principles of the present invention is representatively illustrated. An orienting lock or upper portion 52 of the assembly 50 is utilized to releasably secure and rotationally orient the assembly within a wye block housing assembly described in further detail below. A guide or lower portion 54 of the assembly 50 is utilized to permit access to a selected string attached to the wye block housing assembly, and to exclude access to other strings attached to the wye block housing assembly. Of course, it is not necessary for the upper portion 52 to be above the lower portion 54 , or for the access control assembly 50 to be otherwise constructed exactly as depicted in FIGS. 2A-2C, in keeping with the principles of the present invention.
The upper portion 52 includes a series of circumferentially spaced apart keys 56 which are biased outwardly by a corresponding set of springs 58 . The keys 56 are shaped so that they will cooperatively engage a latching profile formed internally in the wye block housing assembly described below. An internal sleeve 60 maintains the keys 56 in engagement with the latching profile when the sleeve is in its downwardly disposed position as depicted in FIG. 2 A. Note that the sleeve 60 is threadedly attached to a tubular upper connector 62 having an internal profile 64 formed therein so that, when it is desired to retrieve the assembly 50 from within the wye block housing assembly, the upper connector may be engaged by an appropriately configured retrieval tool (not shown) which displaces the upper connector and sleeve upwardly, thereby permitting the keys 56 to retract out of engagement with the wye block housing assembly and permitting the assembly to be retrieved from the well.
An orienting key 66 of the upper portion 52 is, however, not configured for cooperative engagement with the wye block housing assembly latching profile. Instead, the orienting key 66 is configured for engagement with an orienting profile of the wye block housing assembly, described more fully below. In a unique aspect of the present invention, the orienting key 66 is rotationally oriented relative to the lower portion 54 prior to conveying the assembly 50 into the wye block housing assembly.
To orient the key 66 relative to the lower portion 54 , a threaded hole 68 formed through an inner tubular mandrel 70 is aligned with one of a series of circumferentially spaced apart openings 72 (only one of which is visible in FIG. 2A) formed through an outer sleeve 74 . The key 66 extends outwardly through the sleeve 74 . Thus, by installing a screw 76 in the opening 72 and threading it into the hole 68 , the sleeve 74 is rotationally secured relative to the mandrel 70 , thereby rotationally securing the key 66 relative to the mandrel.
The lower portion 54 is threadedly attached to the mandrel 70 and is rotationally secured relative thereto by means of one or more set screws 78 . Before securement with the set screws 78 , proper alignment of the lower portion 54 with the mandrel 70 is ensured by alignment of indicator marks or holes 80 , 82 formed on the lower portion and mandrel.
It may now be seen that, by selecting an appropriate one of the openings 72 in which to install the screw 76 , the lower portion may be conveniently rotationally oriented with respect to the key 66 . For example, if it is desired to select from among two tubular string connections spaced 180 degrees apart in the wye block housing assembly for access thereto, two openings 72 may be correspondingly provided in the outer sleeve 74 spaced 180 degrees apart, so that the lower portion 54 may be oriented in either of two rotational positions spaced 180 degrees apart with respect to the key 66 . If it is desired to select from among three tubular string connections spaced 120 degrees apart in the wye block housing assembly for access thereto, three openings 72 may be correspondingly provided in the outer sleeve 74 spaced 120 degrees apart, so that the lower portion 54 may be oriented in one of three rotational positions spaced 120 degrees apart with respect to the key 66 . It will be readily appreciated that a wide variety of relative rotational orientations may be achieved by providing various numbers and spacings of the openings 72 . In addition, it is to be clearly understood that methods of orienting the upper portion 52 relative to the lower portion 54 in keeping with the principles of the present invention are not limited to those representatively described herein, since they are given for illustrative purposes only. For example, instead of providing multiple spaced apart openings 72 , multiple spaced apart threaded holes 68 could be provided, the key 66 could be selectively oriented with respect to the lower portion 54 by utilizing differently configured sleeves 74 , mandrels 70 , or combinations thereof, etc.
The lower portion 54 includes an inclined guide surface 84 formed in a guide structure 86 which has an upper generally tubular end 88 and a lower generally cylindrical end 90 . The upper tubular end 88 is threadedly attached and rotationally secured to the upper portion 52 as described above. The lower end 90 is configured to be received within the wye block housing assembly as described below, in a manner restricting lateral displacement of the guide structure 86 relative to the wye block housing assembly. For this purpose, the lower end 90 has a generally conical shape, but may be otherwise configured without departing from the principles of the present invention.
Referring additionally now to FIGS. 3A-3E, a wye block or access control apparatus 100 embodying principles of the present invention is representatively illustrated. The wye block 100 may be utilized for the wye block 12 in the method 10 described above. Of course, the method 10 may be performed utilizing a wye block or access control apparatus other than the wye block 100 , and the wye block 100 may be used in methods other than the method 10 , without departing from the principles of the present invention.
As depicted in FIGS. 3A-3E, the wye block 100 has the access control assembly 50 operatively installed therein. When used in the method 10 , it will be appreciated that the access control assembly 50 is not installed in a housing assembly 102 of the wye block 100 until it is desired to access a selected one of tubular strings attached to the housing assembly. Additionally, once such access is no longer desired, the assembly 50 may be retrieved from within the housing assembly 102 , so that flow therethrough is not impeded, debris does not accumulate about the access control assembly, the access control assembly does not deteriorate, etc.
The orienting key 66 of the access control assembly 50 has engaged a generally helically-shaped orienting profile 104 in the housing assembly 102 , thereby rotationally orienting the access control assembly 50 relative to the housing assembly. The orienting profile 104 is formed on a sleeve 106 secured within the housing assembly 102 . When the access control assembly 50 is lowered into the housing assembly 102 , the orienting key 66 engages the orienting profile 104 and rotates the access control assembly 50 relative to the housing assembly 102 . Thus, the orienting key 66 and the orienting profile 104 may be considered portions of an overall orienting device for rotationally positioning the guide structure 86 relative to the housing assembly 102 .
At the lower end of the orienting profile 104 a substantially vertical slot 108 receives the orienting key 66 and prevents further rotation of the access control assembly 50 within the housing assembly 102 . At this time, the other keys 56 engage a cooperatively shaped internal latching profile 110 formed in the sleeve 106 . The upper connector 62 and inner sleeve 60 of the access control assembly 50 are then displaced downwardly relative to the remainder of the upper portion 52 , thereby securing the access control assembly within the housing assembly 102 .
It may now be fully appreciated that, when the access control assembly 50 is operatively installed within the housing assembly 102 , the guide structure 86 is automatically aligned with a selected one of two lower tubular string connections 112 , 114 formed on the housing assembly. As shown in FIGS. 3D & 3E, the guide surface 84 is positioned to deflect a tool, equipment, etc. into the connection 114 , while the remaining tubular portion of the guide structure 86 prevents access to the other connection 112 . It will also be appreciated that, if the screw 76 were installed in another opening 72 spaced 180 degrees apart from the opening 72 shown in FIG. 3C, the guide surface 84 would be positioned to deflect a tool, equipment, etc. into the connection 112 , while the remaining tubular portion of the guide structure 86 would prevent access to the other connection 114 .
The lower end 90 of the guide structure 86 is received in a cooperatively shaped recess 116 , thereby preventing undesirable lateral deflection of the guide structure 86 within the housing assembly 102 , while permitting rotation of the access control assembly 50 as it is installed in the housing assembly.
At the upper end of the housing assembly 102 , an upper tubular string connection 118 is provided. Each of the connections 112 , 114 , 118 may be provided with threads, seals, etc. as needed for interconnection of the wye block 100 to tubular strings in a well. For example, the upper connection 118 could be connected to the string 14 , and the lower connections 112 , 114 could be connected to the strings 16 , 18 , in the method 10 described above.
Of course, many modifications, additions, substitutions, deletions and other changes to the specific embodiments of the present invention described above will be readily apparent to one skilled in the art upon consideration of the above description, and such changes are contemplated by the principles of the present invention. Accordingly, the foregoing detailed description is to be clearly understood as being given by way of illustration and example only, the spirit and scope of the present invention being limited solely by the appended claims.
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A subterranean well completion system and associated methods of servicing wells provide convenient access to selected ones of multiple tubing strings installed in wells. In a described embodiment, a completion system includes a wye block device which has an access control assembly separately conveyed into a housing assembly installed in a well. The access control assembly is conveyed into the housing assembly when it is desired to access a selected one of multiple tubing strings attached to the housing assembly.
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The present invention relates to a unit for the transfer and distribution of a liquid and a method of manufacturing the same according to claims 1 respectively 12 . The invention further relates to a refill for a dispenser for volatile liquids.
BACKGROUND OF THE INVENTION
In order to transfer liquids it is known to use capillary action which is dependent on the cohesive forces within the liquid and the adhesive forces of the liquid to a capillary medium comprising small channels, e.g. pores or spaces between fibers. Such a capillary medium, e.g. a wick, being introduced through an opening into a reservoir, can therefore be used to draw a liquid out of said reservoir passively by means of capillary action only, i.e. without additional sucking. The transferred liquid may be used to distribute chemical substances to the ambient air in order to generate or mask an odour, to evoke a medical or organoleptic effect or to affect insects.
The U.S. Pat. No. 5,114,625 discloses a fragrance dispenser with a liquid reservoir and a wick with a liquid receiving end disposed in the reservoir for drawing liquid therefrom into the wick. A portion of the wick length is exposed to an air flow provided by a fan.
However, the distribution of volatile chemical substances contained in the liquid in the air flow is not sufficiently homogenous when the air flow is brushing over the wick. Further, in most cases dispensing a substance cannot be done without generation of an external air flow in order to evaporate a given amount of liquid per unit time.
The wicks used in prior art dispensing devices are difficult to exchange as they have to be mounted in such a way that the wick is arranged in a defined position relative to the reservoir. This is rendered difficult as wicks are generally soft. Further, the reservoir including the wick has to be tight to prevent spilling of the liquid and uncontrolled evaporation. The same problem arises with a refill for such a device. A refill already including a wick has to be tightly sealed before use, while refill and wick separated from each other have to be such that the wick is easy and clean to insert and the refill is tight before and during use.
It is therefore an object of the invention to provide a unit for the transfer and distribution of a volatile liquid that has a good efficiency in evaporating liquid, is easy and cheap to manufacture and is easily and hygienically insertable into a reservoir, especially the reservoir of a refill.
It is another object of the invention to provide a method of manufacturing such an improved transfer unit.
It is a further object of the invention to provide a refill suited for the use with such a transfer unit.
SUMMARY OF THE INVENTION
The above and other objects of the invention are achieved by a transfer unit as specified in claim 1 , a method of manufacturing the same as specified in claim 12 , a refill and a dispenser with such a transfer unit and such a refill.
According to the invention a shaft comprising a first capillary medium to draw a liquid into the shaft due to capillary action, e.g. a wick, scrib rod or a porous rod, is provided with an integrated screen to serve as an enlarged liquid receiving area from which the liquid is easily evaporated to the ambient air. To provide an enlarged area, the screen is preferably at least two to three times as wide as the shaft. By capillary action the liquid is drawn from the shaft to the screen and distributed over it, using a second capillary medium connected to the first capillary medium. As first capillary medium in general any material capable of absorbing and transferring a liquid due to capillary action is suited, e.g. material containing natural or synthetic fibers, woven or non-woven fabrics, porous media, capillary tubes, or a rod with external grooves, e.g. as described in U.S. Pat. No. 4,913,350. As second capillary medium a material with open pores from which liquid evaporates is suited, e.g. material containing natural or synthetic fibers, woven or non-woven fabrics, porous media. In a preferred embodiment first and second capillary medium are a single piece, for example shaft and screen are made of a sheet of card board or non-woven welded or laminated material, which is cheap and therefore suited for the production of a mass article. Shaft and screen are preferably rigid to maintain the shape of the transfer unit and its position with respect to the reservoir when introduced into the dispenser.
In a preferred embodiment of the invention the screen is permeable to air flow through the screen in a direction approximately normal to the plane of the screen. This can be achieved by a screen having one or more openings. In one preferred embodiment there are a plurality of “small” openings, each with an area less than 5% of the total screen area, distributed preferably uniformly over the screen and result in openings in the screen totalling no more than 95%. By the screen material itself being capillary at least between the openings the liquid is distributed over the screen and around the openings where it evaporates. Additionally or alternatively, the openings or the whole screen area can be covered with another air permeable capillary medium, such as a gauze sheet or tissue paper, which additionally respectively solely receives and distributes the liquid. In this case there is not need for the openings being “small”, i.e. one or more “bigger” openings each with an area of equal to or greater than 5% of the total screen area can be used to transmit the air. To enhance evaporation, an externally generated air flow is advantageous but not essential.
The refill according to the invention comprises a reservoir containing the liquid, an outlet opening and a shaft receiving passage starting at the outlet opening and projecting inward. The shaft receiving passage is suitable for receiving the shaft of the transfer unit as described above. Preferably the receiving passage is dimensioned to tightly embrace the shaft, as this stabilizes the transfer unit and a capillary effect can be achieved between the shaft and the walls of the receiving passage enhancing the capillary action of the shaft itself. Another embodiment of the shaft may be envisaged where lower capillary action is required. This can be achieved through tapering of the shaft for the lower portion of ist length, such that it is not in intimate contact wiht the lower portion of the receiving passage. The refill and the shaft receiving passage may be moulded in one piece which can be produced at low cost. In a preferred embodiment the shaft receiving passage comprises a seal, e.g. a metal foil, plastic moulding, or any inpervious material that can be easily punctured isolating the liquid in the reservoir from the outside. Preferably, the seal is located at the bottom end of the passage and may be punctured by the shaft when fully introduced into the refill. A commercial embodiment of this could have the shaft partially introduced into the shaft receiving passage and the action of inserting the refill into the main unit causes the shaft to break the seal. To facilitate breaking the seal the shaft preferably comprises a cutting member at its bottom portion, e.g. a tip or a thorn or a knife-like element. Seal location at the bottom end of the passage is advantageous as the narrow passage protects the seal against accidental damage. The refill can thus be sold ready for use without an extra cover of the outlet opening, such as a lid, thus saving material, waste and manufacturing costs. Introduction of the shaft can be accomplished without spilling.
The transfer unit is preferably sold in a blister package containing one or more transfer units or a refill and an isolated unit insertable into the refill.
A coating of the lateral shaft faces respectively a layer around these faces impermeable to liquid is advantageous as it prevents softening of the shaft and stabilizes the shaft. Further, it enables the control of the dispensed amount as liquid flow can be stopped by tilting or turning the reservoir, thus preventing contact of the bottom portion with the liquid.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a transfer unit with a shaft and a screen with a plurality of “small” openings;
FIG. 2 shows a transfer unit with a shaft and a screen both having a plurality of “small” openings;
FIG. 3 shows a transfer unit with a shaft and a screen having one “big” opening;
FIG. 3A shows a generic shaft which may have screens as depicted in FIGS. 1-3, but has tapered lower portion;
FIGS. 4 a-c shows different views of a shaft receiving passage;
FIGS. 5 a,b shows the insertion of a transfer unit into the shaft receiving passage of FIGS. 4 a-c;
FIGS. 5 c,d shows a view of a shaft receiving passage with the tapered shaft as shown on FIG. 3A
FIGS. 6 a,b shows a refill with a transfer unit;
FIG. 7 shows one method of manufacturing the transfer units as shown in FIG. 1;
FIG. 8 a shows an example of a perforated sheet as a sheet material for transfer units as shown in FIG. 2;
FIG. 8 b shows a method of manufacturing transfer units as shown in FIG. 2 using the sheet of FIG. 8 a;
FIGS. 9 a,b and c shows a method of manufacturing transfer units as shown in FIG. 3 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows a transfer unit 1 with an elongated shaft 2 and a screen 3 . The shaft 2 consists of a first capillary medium 4 , here absorbent card board 4 ′, preferably 1 to 4 mm thick. The shaft 2 may have, but is not restricted to a rectangular shape with a width W 1 of preferably 5 to 10 mm. The length of the shaft 2 is greater than the width W 1 and is chosen such that at least the bottom portion 20 of the shaft 2 is in contact with the liquid, e.g. a perfume, when introduced into a liquid reservoir. The bottom portion 20 has a tip 20 ′ to facilitate breaking a seal, as shown in FIG. 5 a,b . The screen 3 consists of a second capillary medium 5 with a plurality of “small” openings 6 punched out to allow air to pass through, each opening 6 covering less than 5% of the total screen area. The width W 2 of the circular screen 3 is about three times the width W 1 of the shaft 2 . Screen 3 and shaft 2 are made of the same material, a card sheet, i.e. in this embodiment for the second capillary medium 5 the same material as for the first capillary medium 4 is used. Alternatively, different capillary materials could be connected to enable liquid transfer to the screen 3 .
FIG. 2 shows another example for a transfer unit 7 with a shaft 8 and a screen 9 both having a plurality of “small” openings 12 ′, 12 ′. Its shape is generally the same as of the unit of FIG. 1 . As a capillary material for the capillary media 11 and 10 of screen 9 respectively shaft 8 an absorbent card 10 ′ with perforations that constitute the openings 12 , 12 ′ is used, e.g. as shown in FIG. 8 a.
FIG. 3 shows a third example for a transfer unit 13 with a shaft 14 and a screen 15 . The screen 15 comprises an annular frame 18 with a central opening 17 , that covers approximately 80% of the screen area (“big” opening). The opening 17 is covered with a sheet of capillary air permeable material, here a gauze sheet 19 ′. The gauze sheet 19 ′ receives as a second capillary medium 19 liquid drawn into the shaft 14 and to the screen 15 by the first capillary medium 16 . The frame 18 is made of the same material as the shaft 14 , here card board 16 , i.e. the frame contributes to the distribution and transfer of the liquid to the gauze sheet 19 ′ using capillary action. FIG. 3A shows a transfer unit 1 ′ with an elongated shaft 2 ′ and a screen 3 . The shaft 2 ′ consists of a first capillary medium 4 ′ preferably 1 to 4 mm thick. The shaft 2 ′ has a rectangular shape at its upper most portion directly below the screen, and a triangular taper for the remainder of its length with the taper comprising of 5% to 95% of the total length of the shaft. The length of shaft 2 ′ is greater than the maximum width and is chosen such that at least the bottom portion of the shaft is in contact with the liquid.
In another embodiment (not shown) the frame 18 is made of a non capillary material, such as plastic or metal, serving to stabilise the second capillary medium 19 which is connected to the shaft for liquid transfer. In yet another embodiment (not shown) the shaft itself comprises a frame made of non capillary material stabilising a first capillary medium, e.g. a gauze sheet or a tissue paper, being connected to the second capillary medium, preferably the second capillary medium being an integral part of the first capillary medium.
FIGS. 4 a-c shows different views of a shaft receiving passage 21 dimensioned to receive the shaft of a transfer unit. A transfer unit 1 being introduced into the receiving passage 21 is shown in FIGS. 5 a,b . The receiving passage 21 may be an integral part of a refill for an air freshener or the like, as shown in FIGS. 6 a, b , or may be suited for insertion into the outlet opening of a liquid reservoir.
The receiving passage 21 comprises an elongated sleeve 23 having a rectangular cross section dimensioned to tightly embrace the shaft 4 of transfer unit 1 . The receiving passage 21 further comprises a fitting 22 adjacent to the sleeve 23 having circular cross section. The fitting is dimensioned to tightly fit into a circular outlet opening of a liquid reservoir 26 . The fitting 22 comprises an annular flange 35 to seal the outlet opening when the passage 21 is inserted. In case the receiving passage is an integral part of the liquid reservoir 26 the fitting 22 is not essential as the passage 21 and the reservoir 26 can be moulded in one piece. The passage 21 guides the transfer unit 1 into a defined position with respect to the dispensing device, e.g. to a fan generating an air flow. In this position transfer unit 1 is mechanically stabilised by passage 21 .
FIGS. 5 c-d are similar to FIGS. 4 b-c except that they depict a shaft receiving passage 23 ′ containing a tapered shaft 2 ′, as shown in FIG. 3 a . The receiving passage has a cross section dimensioned as not to tightly embrace the shaft 2 ′ hence leaving a gap between the shaft and receiving passage of at least 1 mm on both front and back sides. In this embodiment there will be a tight fitting portion at the top 36 ′ of the receiving passage 23 ′ to hold the transfer unit 9 ′ in place.
The bottom opening of the passage 21 is closed with a foil seal 24 that can be punctured by the shaft 4 as shown in FIGS. 5 b and 6 b . The seal 24 isolates the liquid 27 contained in the reservoir 26 of the refill 25 from the outside, no extra lid is needed. When the transfer unit 1 is inserted, the tip 20 ′ of its bottom portion 20 breaks the seal 24 , the liquid 27 has access to the shaft 4 immediately, is drawn up to the screen 3 and evaporated.
FIGS. 7, 8 b and 9 a-c show methods of manufacturing the transfer units as shown in FIGS. 1 to 3 . The transfer unit of FIG. 1 is manufactured by punching a shape 29 with a circular main body 29 ′, forming the screen afterwards, and an elongated part 29 ″, forming the shaft, from a sheet 28 of capillary material. This shape 29 can be punched in one go with a plurality of holes 29 ′″ arranged within the main body shape 29 ′ or before or after punching the holes 29 ′″.
A pre-perforated sheet or mat 30 of capillary material with a plurality of holes 31 as shown in FIG. 8 a serves as basis for manufacturing transfer units shown in FIG. 2. A shape 29 as described above is punched from the sheet 30 . The cut out shape is ready to use as a transfer unit.
The steps of an alternative manufacturing method are depicted in FIGS. 9 a-c , where “big” holes 33 are punched from a continual mat or sheet 32 (FIG. 9 a ). Then a strip of continual air permeable capillary material 34 such as gauze is glued over the holes 33 (FIG. 9 b ). A shape 29 as described above is punched from the sheet 32 , where the shape 29 is positioned such that each hole 33 is located in the center of the circular main body 29 ′.
The inventive transfer units 1 , 7 , 13 as shown above can thus be manufactured at very low cost as the materials used, e.g. gauze, cardboard, fleece, are cheap and the methods of manufacturing described in FIGS. 7 to 9 involve three steps at most.
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A unit ( 1 ) for the transfer and distribution of the liquid ( 27 ) using capillary action has an elongated shaft ( 2 ) and a screen ( 3 ). The shaft ( 2 ) includes a first capillary medium ( 4 ) suitable for drawing the liquid ( 27 ) from a reservoir ( 26 ) into the shaft ( 2 ) when a bottom portion ( 20 ) of the shaft ( 2 ) is disposed in the liquid. The screen ( 3 ) is connected to the shaft ( 2 ) and includes a second capillary medium ( 5 ) suitable for receiving the liquid ( 27 ) drawn by the first capillary medium ( 4 ) and distributing it over at least a major part of the screen ( 3 ) where it evaporates.
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CROSS REFERENCE TO RELATED APPLICATION
This application is a Divisional of U.S. patent application Ser. No. 14/203,224 filed on Mar. 10, 2014, which claims priority under 35 U.S.C. §119(a) to Patent application No. 102119875 filed in Taiwan on Jun. 5, 2013, all of which are hereby expressly incorporated by reference into the present application.
TECHNICAL FIELD
The present disclosure relates to a method and a pharmaceutical composition for hair growth.
BACKGROUND
Alopecia is a syndrome of loss of hair resulting from the decrease of hairs in the anagen phase of a hair growth cycle and from the increase of hairs in the catagen phase or telogen phase of the hair growth cycle. Although the mechanism of alopecia is unclear, a lot of factors causing alopecia might be endocrine disorder, hormone unbalance, autonomic nerves disorder, circular disorder, excessive sebum due to the abnormal blood circulation, degeneration of skin due to fungi, allergy, genetic disorder or aging.
Alopecia is one of most serious side effects in cancer that is induced by various chemotherapeutic agents. Since these chemotherapeutic agents interrupt cytokinesis, the chemotherapeutic agents will induce side effects in the tissues, where cytokinesis frequently occurs, including bone marrow, hair follicle, fingernail, toenail, skin and gastrointestinal tract. Thus, the chemotherapeutic agents induce alopecia. Most of patients (80% or above) regard alopecia as the most painful effect in their chemotherapy. The need for treating alopecia due to the chemotherapy is still strong and not fulfilled.
Alopecia occurs in two to four weeks after the treatment of chemotherapy. Hair will grow during three to six months after the chemo-treatment. The degree of alopecia depends on the types of chemotherapeutic agents, the dosage thereof and the schedule of administration. Those agents inducing serious alopecia include cyclophosphamide, doxorubicin, cisplatin, cytosine arabinoside and etoposide. The above-mentioned agents induce alopecia even if those are administrated in partial area of the skin. In other words, the chemotherapeutic agents affect the cytokinesis of the hair follicle that induces apoptosis of the follicle cells or converts the anagen phase of the follicle cells into the catagen phase.
Currently, the clinic approaches for alopecia includes applying external medicine on the hair follicle, orally administrating medicine, and hair implantation. Minoxidil and Finasteride are two kinds of medicine for growth hair that are approved by FDA. Patients with alopecia are often required to continuously administrate Minoxidil for external use and the Finasteride for internal use. In addition, Minoxidil and Finasteride may only reduce the loss of hair instead of increasing the number of hair follicles. Moreover, since Minoxidil and Finasteride have several side effects such as sexual dysfunction, hypertrichosis, and fetus defect, none of the medicines can be administrated for pregnant women. Furthermore, hair implantation may leave scars, require a long recovering period, and cost a lot due to several times of surgery.
SUMMARY
The present disclosure provides a method for hair growth. The peptide is a hair growth peptide (HGP), which includes all or part of an amino acid sequence: PSTHVLITHTI (SEQ ID No: 1).
The present disclosure provides a method for hair growth. The peptide is HGP. A similarity between a sequence of the HGP and an amino acid sequence PSTHVLITHTI (SEQ ID No: 1) are 90% to 99%. The similarity is obtained by the software shimadu LCMS2010 for sequence analysis.
The present disclosure provides a pharmaceutical composition for the treatment of alopecia. The pharmaceutical composition includes a hair growth peptide (HGP) and a phosphate salt. The HGP includes all or part of an amino acid sequence: PSTHVLITHTI (SEQ ID No: 1).
The present disclosure provides a pharmaceutical composition for the treatment of alopecia. The pharmaceutical composition includes a hair growth peptide (HGP) and a phosphate salt. A similarity between a sequence of the HGP and an amino acid sequence PSTHVLITHTI (SEQ ID No: 1) are 90% to 99%.
Another function of the present disclosure will be described at following paragraphs. Certain functions can be realized in present section, while the other functions can be realized in detailed description. In addition, the indicated components and the assembly can be explained and achieved by detail of the present disclosure. Notably, the previous explanation and the following description are demonstrated instead of limiting the scope of the present disclosure.
The foregoing has outlined rather broadly the features and technical benefits of the disclosure in order that the detailed description of the disclosure that follows may be better understood. Additional features and benefits of the disclosure will be described hereinafter, and form the subject of the claims of the disclosure. It should be appreciated by those skilled in the art that the conception and specific embodiment disclosed may be readily utilized as a basis for modifying or designing other structures or processes for carrying out the same purposes of the disclosure. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the disclosure as set forth in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and, together with the description, serve to explain the principles of the invention.
The foregoing summary, as well as the following detailed description of the invention, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there are shown in the drawings examples, which are presently preferred. It should be understood, however, that the invention is not limited to the precise arrangements and instrumentalities shown.
A more complete understanding of the present disclosure may be derived by referring to the detailed description and claims when considered in connection with the Figures, where like reference numbers refer to similar elements throughout the Figures, and:
FIG. 1 shows a schematic view of a schedule of an experiment in accordance with an embodiment of the present disclosure;
FIG. 2 illustrates a schematic view of six sections on dorsal skin of the mouse in accordance with an embodiment of the present disclosure;
FIG. 3 illustrates a schematic view of an immuno-fluorescent staining, which shows that the marker CK15 of the hair follicle stem cells is obviously activated after the follicle stem cells are treated with the SEQ ID No: 1 peptide. Thus, the SEQ ID No: 1 peptide enables activation of the regeneration of the hair follicle stem cells;
FIG. 4 illustrates a schematic view of an immuno-fluorescent staining in accordance with Wnt3a marker. In order to realize how the SEQ ID No: 1 peptide activates the follicle stem cells to regenerate hair growth, the immuno-fluorescent staining is used to analyze whether Win/β-catenin signal transduction pathway is activated or not. As indicated by the arrows in FIG. 4 , Wnt3a is obviously activated in the hair follicle stem cells;
FIG. 5 illustrates a schematic view of an immuno-fluorescent staining in accordance with β-catenin marker. Since β-catenin is a downstream gene of Wnt signal transduction pathway, activating β-catenin allows initiation of a Wnt signal transduction pathway so as to regenerate the hair follicle stem cell. In FIG. 5 , the SEQ ID No: 1 peptide is observed to have effect on activating or regenerating the hair follicle stem cells;
FIG. 6 illustrates a schematic view of a TCF reporter assay in Human Hair Follicular Keratinocytes (HHFK) cell line. TOP represents that the reporter gene has a functional binding site where β-catenin is bound. FOP represents that the functional binding site of the reporter gene is mutated and hence β-catenin cannot bind on the binding site and acts as a negative control. CTL represents that HHFK cell line is not treated with any stimulant. iPept-1 means that HHFK cell line is treated with the SEQ ID No: 1 peptide. In view of the relative luciferase activity, HHFK cell line with the treatment of the SEQ ID No: 1 peptide is observed to increase the activity of β-catenin;
FIG. 7 illustrates a schematic view of a TCF reporter assay in HaCaT Keratinocyte cell line. TOP represents that the reporter gene has a functional binding site where β-catenin is bound. FOP represents that the functional binding site of the reporter gene is mutated and hence β-catenin cannot bind on the binding site and acts as a negative control. CTL represents that HaCaT Keratinocytes are not treated with any stimulant. iPept-1 means that HaCaT Keratinocytes are treated with the SEQ ID No: 1 peptide. In view of the relative luciferase activity, HaCaT Keratinocytes with the treatment of the SEQ ID No: 1 peptide are observed to increase the activity of β-catenin;
FIG. 8 illustrates a result of RT-PCR analysis in macrophages. Ctl represents that macrophages are not treated with any stimulant. iPept-1 means that macrophages are treated with the SEQ ID No: 1 peptide. According to the result, the SEQ ID No: 1 peptide is useful to activate the gene expression of Wnt16 and Wnt7b in macrophages; and
FIG. 9 illustrates a result of QRT-PCR analysis in macrophages. CTL represents that macrophages are not treated with any stimulant. iPept-1 means that macrophages are treated with the SEQ ID No: 1 peptide. According to the result, the treatment of SEQ ID No: 1 peptide enhances the gene expression of Wnt16 in macrophages.
DETAILED DESCRIPTION
In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments. It will be apparent, however, that one or more embodiments may be practiced without these specific details. In other instances, well-known structures and devices are schematically shown in order to simplify the drawing.
In addition, the following embodiments can be properly integrated to complete another embodiment. References to “modified embodiment,” “the embodiment,” “other embodiments,” “another embodiment,” etc. indicate that the embodiment(s) of the disclosure so described may include a particular feature, structure, or characteristic, but not every embodiment necessarily includes the particular feature, structure, or characteristic. Further, repeated use of the phrase “in the embodiment” does not necessarily refer to the same embodiment, although it may.
The present disclosure is directed to a method for the hair growth and a pharmaceutical composition for the treatment of alopecia. In order to make the present disclosure completely comprehensible, detailed steps and structures are provided in the following description. Obviously, implementation of the present disclosure does not limit special details known by persons skilled in the art. In addition, known structures and steps are not described in details, so as not to limit the present disclosure unnecessarily. Preferred embodiments of the present disclosure will be described below in detail. However, in addition to the detailed description, the present disclosure may also be widely implemented in other embodiments. The scope of the present disclosure is not limited to the detailed embodiments, and is defined by the claims. The following description of the disclosure accompanies drawings, which are incorporated in and constitute a part of this specification, and illustrate embodiments of the disclosure, but the disclosure is not limited to the embodiments.
The molecular weights of the peptides and the hair growth peptide (HGP) of the present disclosure are confirmed, but not limited, by a mass spectrometry. For instance, the present disclosure utilizes Time-of-Flight mass spectrometry, Sciex QSTAR PULSAR Quadrupole (purchased from Applied Biosystems) to confirm the molecular weight. The sample in appropriate amount is dissolved in a formic acid solution to form a sample solution. Under a special condition, protease such as serine proteases, threonine proteases, cysteine proteases, aspartate proteases, glutamic proteases and metalloproteases are used to cut the sample into several fragments, which is dissolved in the formic acid solution in order to complete a sample solution. 5 μl of the sample is injected into the foregoing mass spectrometry. After the mass spectrometry completes the measurement, the spectrogram from the mass spectrometry is analyzed by software such as shimadu LCMS2010 to confirm the target peptide(s) in the spectrogram. One approach to verify the target peptide in the spectrogram is to check the mass-to-charge ratios of at least two peaks, which fall within the range of the target peptide. The other approach is to check the difference between the mass-to-charge ratio of the target peptide and the mass-to-charge ratio of the peaks in the spectrogram. For instance, the molecular weight of amino acid sequence SEQ ID No: 1 is 1218.43. When the peptide carries two electric charges, the mass-to-charge ratio is about 610.15 ((1218.43+2)/2). The mass-to-charge ratio (m/z) is equal to the total mass (including the mass M of peptide and the mass N of the electron)/total electric charge. Thus, while the peak labeled with a mass-to-charge ratio about 610.15 is found in the spectrogram, it is confirmed that the peptide, which has an amino acid sequence the same with the SEQ ID No: 1 sequence, exists in the sample solution. In addition, the molecular weights of the other amino acid sequences are referred to the table 1.
Similarly, the sample solution of the pharmaceutical composition is prepared by the above-identified process to confirm whether the peptide exists in the pharmaceutical composition. In some embodiments, the sample solution of the pharmaceutical composition is diluted and then proceeds with the foregoing process.
The phosphate salt of the pharmaceutical composition in the present disclosure is selected from KH 2 PO 4 , Na 2 HPO 4 .2H 2 O and a combination thereof.
In some embodiments, the pharmaceutical composition of the present disclosure includes excipients, which increase the uniformity and stability of the composition and decrease the irritation and stink of the composition. The excipients of the present disclosure are non-toxic, non-irritant, non-antigenic, non-allergic, non-mutagenic and non-pharmacoactive and do not interfere pharmacodynamics of the composition.
Accordingly, the excipients of the present disclosure are selected from lactose, starch, starch paste, dextrin, cyclodextrin, pregelatinized starch, carboxymethyl starch sodium, hydroxypropy starch, microcrystalline cellulose, carboxy methyl cellulose, cross-linked carboxymethy cellulose sodium, low substituted hydroxypropyl cellulose and a combination of the at least two foresaid excipients.
The identification method for the excipients is selected from chromatography methods, spectrophotometry methods, spectroscopy methods and titrimetric methods.
The hair growth peptides (HGP) in the present disclosure or in the pharmaceutical composition are synthesized, but not limited, by the solid phase peptide synthesis, which is also known as Merrifield method. In some embodiments, the hair growth peptides (HGP) in the present disclosure or in the pharmaceutical composition are purified through protein expression system. Since the solid phase peptide synthesis is a well-known process, the process detail is referred to any related art. In addition, the HGP of the present disclosure is synthesized by Kelowna Company, which allows persons having ordinary skill in the art to prepare the HGP fragments.
The pharmaceutical composition of the present disclosure can be, but not limited to, a solution dosage form. The HGP is dissolved in 4 ml to 8 ml of Phosphate buffer saline (PBS) solution to form 2 mM HGP solution. In some embodiments, the 2 mM HGP solution is diluted to 0.2 mM HGP solution for the preparation of the pharmaceutical composition of the present disclosure.
The experimental model of the present disclosure is derived from the mouse model of the hair regeneration, which is studied by Dr. Chuong in University of Southern California.
The mouse model adopts female C57BL/6 mice (about 8 weeks).
In accordance with the reports (Muller-Rover et al., 2001; Plikus et al., 2009), after the hair removal on the dorsal skin of the female C57BL/6 mice by wax or uprooting, the hair follicles enter the anagen phase on the seventh day from hair removal. At this time, the dorsal hair will regenerate during the anagen phase, which continues fourteen days. Such step synchronizes all follicles on the dorsal skin.
The hair follicles on the dorsal skin enter the refractory telogen phase through the anagen phase. The refractory telogen phase continues twenty-eight days. In the present disclosure, the sample solution is applied on the dorsal skin, where the hair follicle stays at the refractory telogen phase, to observe whether the peptides are beneficial to hair growth.
In some embodiments shown in FIG. 1 , after the hair removal of the dorsal skin, the new growth hair is removed again at twenty first day after the first hair removal. As shown in FIG. 2 , the dorsal skin where the hair is removed is divided into six sections, each of which is spaced out 3 centimeters apart in avoidance of cross-interference. The sample solution is applied on each of the sections for 10 days. The administration of the sample solution includes, but not limited to, the injection (50 μl) and the coating (10 μl). In addition, the dosage of the sample solution includes, but not limited to, the high dosage level (2000 μM) and the low dosage level (200 μM).
In order to avoid experimental error due to manual operation, a positive control and a negative control are predetermined on two sections. For instance, as referred in FIG. 2 , the first section 1 is continuously coated with cyclosporine for 10 days (once a day, 10 μl a day). The cyclosporine is regarded as the positive control whose concentration is 0.5% by weight. The solvent of the cyclosporine is 100% alcohol. The second section 2 is coated with high dosage level of HGP or the pharmaceutical composition for 10 days (once a day). The third section 3 is coated with low dosage level of HGP or the pharmaceutical composition for 10 days (once a day). The fourth section 4 is coated with 100% alcohol for 10 days (once a day). The fourth section 4 is regarded as the negative control. The fifth section 5 is continuously injected with the high dosage of HGP or pharmaceutical composition for 10 days (once a day). The sixth section 6 is continuously injected with the low dosage of HGP or pharmaceutical composition for 10 days (once a day). The HGP prepared for the sections is the same amino acid sequence.
In accordance with the report (Maurer et al., 1997), if the dorsal skin is coated with cyclosporine for 10 days, the hair of the dorsal skin is induced to regenerate. HGP or pharmaceutical composition having the same as referred at the table 1 is implemented through the above-mentioned process and then the hair regeneration condition is recorded everyday. Since the period of the refractory telogen phase is 28 days, it is regards as a negative result that no hair regeneration is observed at thirtieth day after the administration of the sample solution. The negative result means the peptide cannot improve hair growth. In other words, if the hair regeneration is observed within 30 days after the administration of the sample solution, the peptide or the peptide of the pharmaceutical composition is regarded as HGP, which is able to improve hair growth.
Wnt family has key roles in many developmental processes, including hair follicle growth and differentiation. Canonical Wnt signaling leads to stabilization of β-catenin and accumulation β-catenin, resulting in nuclear translocation and activation of LEF/TCF transcription factors in regulation of gene expression. Wnt/β-catenin signaling has been proposed to function in hair follicle morphogenesis and differentiation (Kishimoto et al. 2000; Fuchs et al. 2001; Millar 2002).
Furthermore, the hair growth cycle is related to Wnt/β-catenin and BMP2/4 signal transduction pathways. Thus, HGP or pharmaceutical composition having the same peptide may control the hair growth through Wnt/β-catenin and BMP2/4 signal transduction pathways. In other words, the HGP or the pharmaceutical composition may affect Wnt/β-catenin and BMP2/4 signal transduction pathways through the hair follicles.
The SEQ ID No. 1 peptide is treated in HHFK, HaCaT and human macrophage to study the hair growth mechanism induced by the SEQ ID No. 1 peptide.
After the female C57BL/6 mice are injected with the SEQ ID No. 1 peptide, the immuno-fluorescent staining with the marker CK15 is performed so as to observe whether the genes, such as Wnt3a, Wnt/β-catenin are activated or not.
In the present disclosure, Human Hair Follicular Keratinocytes (HHFK), HaCaT Keratinocyte and macrophages are used as cell models for realizing the mechanism. Reporter assay and QRT-PCR are used as bioactivity assays to identify how the SEQ ID No. 1 peptide improves hair growth.
Referring to FIG. 3 , the immuno-fluorescent staining shows that the marker CK15 of the hair follicle stem cells is obviously activated after the follicle stem cells are treated with the SEQ ID No: 1 peptide. Thus, the SEQ ID No: 1 peptide enables activation of the regeneration of the hair follicle stem cells. In order to realize how the SEQ ID No: 1 peptide activates the regeneration of the hair follicle stem cells, the immuno-fluorescent staining in accordance with Win/β-catenin signal transduction pathway is performed. As shown in FIG. 4 , Wnt3a is obviously activated in the hair follicle stem cells. Since β-catenin is a downstream gene of Wnt signal transduction pathway, activating β-catenin allows the initiation of a Wnt signal transduction pathway so as to regenerate the hair follicle stem cell. As shown in FIG. 5 , β-catenin is activated by the treatment of the SEQ ID No: 1 peptide. In other words, the SEQ ID No: 1 peptide may activate the Wnt/β-catenin signal transduction pathway to activate the regeneration of the hair follicle stem cells.
In the reporter assay as shown in FIGS. 6 and 7 , a dosage of 50 ng/ml Wnt3a is a positive control. The 200 μM SEQ ID No: 1 peptide is observed to enhance activity of β-catenin in HaCaT and HHFK cells.
After macrophages are treated with the 200 μM SEQ ID No: 1 peptide (iPept-1) for 8 hours, gene regulation of Wnt family (Wnt1, Wnt2, Wnt3a, Wnt4, Wnt6, Wnt7a, Wnt7b, Wnt10a, Wnt10b, Wnt16) are detected by RT-PCR and QRT-PCR tests as shown in FIGS. 8 and 9 . It is observed that the transcription level of Wnt16 and Wnt7b increases in accordance with the treatment of iPept-1. Therefore, the SEQ ID No: 1 peptide is proved to activate Wnt/β-catenin signal transduction pathway so as to regenerate follicle stem cells for hair growth.
Table 1 illustrates the sequence number corresponding to the amino acid sequence.
TABLE 1
Amino acid sequence
Sequence
(from amino terminal
Molecular
number
to carboxyl terminal)
weight
SEQ ID No: 1
PSTHVLITHTI
1218.43
SEQ ID No: 2
HVLIT
581.72
SEQ ID No: 3
VLITH
581.72
SEQ ID No: 4
LITHT
583.69
SEQ ID No: 5
STHVL
555.64
SEQ ID No: 6
PSTHVLITHTISRI
1574.86
SEQ ID No: 7
ITHTI
583.69
SEQ ID No: 8
PSTHVL
652.75
SEQ ID No: 9
PSTHVLI
765.91
SEQ ID No: 10
PSTHVLIT
867.12
SEQ ID No: 11
PSTHVLITH
1004.16
SEQ ID No: 12
PSTHVLITHT
1105.27
SEQ ID No: 13
STHVLITHTI
1121.31
SEQ ID No: 14
THVLITHTI
1034.23
SEQ ID No: 15
HVLITHTI
933.13
SEQ ID No: 16
VLITHTI
795.98
SEQ ID No: 17
LITHTI
696.85
SEQ ID No: 18
PSTHVLGSFGS
1088.19
SEQ ID No: 19
PSTHVLIGSFG
1114.28
SEQ ID No: 20
PSTHVLITGSF
1158.33
SEQ ID No: 21
PSTHVLITHGS
1148.29
SEQ ID No: 22
PSTHVLITHTG
1162.32
SEQ ID No: 23
PSTHVLSFGSG
1088.19
SEQ ID No: 24
PSTHVLIFGSG
1114.28
SEQ ID No: 25
PSTHVLITGSG
1068.20
SEQ ID No: 26
PSTHVLITHSG
1148.29
SEQ ID No: 27
PSTHVLITHTS
1192.35
SEQ ID No: 28
PSTHVLITHTISR
1461.70
SEQ ID No: 29
PSTHVLITHTIS
1305.51
SEQ ID No: 30
GSTHVLITHTI
1178.36
SEQ ID No: 31
GSFHVLITHTI
1224.44
SEQ ID No: 32
GSFGVLITHTI
1144.35
SEQ ID No: 33
GSFGFLITHTI
1192.39
SEQ ID No: 34
GSFGSFITHTI
1166.31
SEQ ID No: 35
FSTHVLITHTI
1268.49
SEQ ID No: 36
FGTHVLITHTI
1238.46
SEQ ID No: 37
FGSHVLITHTI
1224.44
SEQ ID No: 38
FGSFVLITHTI
1234.47
SEQ ID No: 39
FGSFGLITHTI
1192.39
SEQ ID No: 40
FGSFGSITHTI
1166.31
SEQ ID No: 41
PSTHVLLTHTI
1218.43
Table 2 illustrates the experimental numbers of HGP and the pharmaceutical composition corresponding to the sequence numbers. The similarity among the sequences of the present disclosure is analyzed by the software shimadu LCMS2010.
TABLE 2
Experimental number
Sequence number
P1
SEQ ID No: 1
P2
SEQ ID No: 2
P3
SEQ ID No: 3
P4
SEQ ID No: 4
P5
SEQ ID No: 5
P6
SEQ ID No: 6
P7
SEQ ID No: 7
P8
SEQ ID No: 8
P9
SEQ ID No: 9
P10
SEQ ID No: 10
P11
SEQ ID No: 11
P12
SEQ ID No: 12
P13
SEQ ID No: 13
P14
SEQ ID No: 14
P15
SEQ ID No: 15
P16
SEQ ID No: 16
P17
SEQ ID No: 17
P18
SEQ ID No: 18
P19
SEQ ID No: 19
P20
SEQ ID No: 20
P21
SEQ ID No: 21
P22
SEQ ID No: 22
P23
SEQ ID No: 23
P24
SEQ ID No: 24
P25
SEQ ID No: 25
P26
SEQ ID No: 26
P27
SEQ ID No: 27
P28
SEQ ID No: 28
P29
SEQ ID No: 29
P30
SEQ ID No: 30
P31
SEQ ID No: 31
P32
SEQ ID No: 32
P33
SEQ ID No: 33
P34
SEQ ID No: 34
P35
SEQ ID No: 35
P36
SEQ ID No: 36
P37
SEQ ID No: 37
P38
SEQ ID No: 38
P39
SEQ ID No: 39
P40
SEQ ID No: 40
P41
SEQ ID No: 41
The peptides of the experimental number P1 to P41 is adopted in the previously discussed processes as referred in FIG. 1 and FIG. 2 and the hair growth condition is observed and recorded in the table 3. The number x of the hair growth in the table 3 means that the hair regeneration condition is observed at the x'th day after the high dosage level is administrated on the dorsal skin. For instance, the number (x=5) means that the hair growth is observed at fifth day. Furthermore, the symbol NA represents the need for further analysis. Furthermore, each of the number x is verified by the positive control, where the hair regeneration is observed within 30 days. In addition, the “negative” represents no hair growth by using the peptide in accordance with the experimental number.
TABLE 3
Experimental number
Number x
P1
17
P2
17
P3
17
P4
17
P5
19
P6
19
P7
17
P8
15
P9
negative
P10
negative
P11
19
P12
19
P13
negative
P14
negative
P15
negative
P16
negative
P17
22
P18
22
P19
negative
P20
negative
P21
23
P22
23
P23
negative
P24
negative
P25
22
P26
22
P27
negative
P28
negative
P29
22
P30
22
P31
negative
P32
negative
P33
negative
P34
negative
P35
15
P36
15
P37
negative
P38
negative
P39
negative
P40
negative
P41
19
Although the present disclosure and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations could be made herein without departing from the spirit and scope of the disclosure as defined by the appended claims. For example, many of the processes discussed above can be implemented in different methodologies and replaced by other processes, or a combination thereof.
Moreover, the scope of the present disclosure is not intended to be limited to the particular embodiments of the process, sequence, peptide, and 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 disclosure, processes, sequence, peptide, compositions 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 disclosure. Accordingly, the appended claims are intended to include within their scope such processes, sequence, peptide, compositions of matter, means, methods, or steps.
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The present disclosure relates to a method of applying a pharmaceutical composition for promoting hair growth. The pharmaceutical composition includes a hair growth peptide (HGP) which includes all or part of the amino acid sequence SEQ ID No: 1. The method includes administering a hair growth peptide (HGP) which includes all or part of the amino acid sequence SEQ ID No: 1 to an interest.
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BACKGROUND
The invention relates to a backscatter transponder for generating an oscillator signal based on a base signal with an oscillator for actively constructing the oscillator signal by means of oscillations, an input for the base signal and an output for the oscillator signal generated, whereby the oscillator is rendered capable of being activated in a quasi-phase-coherent manner with the aid of a control signal generated by a clock generator and is capable of being activated in a quasi-phase-coherent manner with respect to the base signal by means of the base signal for generating the oscillator signal.
The invention also relates to a communication system incorporating such a backscatter transponder and/or a method for transmitting data with such a backscatter transponder.
Methods and arrangements for exchanging data and for measuring the distance from a base station to a modulated transponder exist in numerous forms and have been known for a long time. Customary transponders comprise what are referred to as “backscatter transponders”, for example, which do not have their own signal source but instead simply reflect back the received signal (where relevant, in amplified form). Reference is also made in this context to “modulated backscatter”.
Although the backscatter transponder constitutes the data transmitter, a dedicated radio frequency signal is not customarily generated in a backscatter transponder. A radio frequency auxiliary carrier signal is sent first from the actual data receiver station to the transponder, which this transponder sends back, usually with low-frequency modulation.
The critical advantage of communication systems based on backscatter transponders with respect to standard communication systems having separate signal sources in all sub-stations therefore consists in the fact that the signal received in the receiver can be restricted to the modulation bandwidth in a virtually optimal manner via mixing with the auxiliary carrier signal and therefore a virtually optimal signal-to-noise ratio is achieved.
With the separate signal sources in the transmitter and receiver which are otherwise customary in communication systems, it is generally not possible, or only with great effort, particularly in the case of lower data rates, to regulate the separate sources in such a precise manner with respect to frequency and phase that a comparably small receiver bandwidth would be achievable.
The critical disadvantage of backscatter transponder systems, however, is the fact that the radio frequency signal has to travel along the path from the receiver to the transponder and back and therefore, based on the radar equation, the signal-to-noise ratio (SNR) for the overall transmission link decreases in proportion to the 4th power of the distance. Due to free field attenuation which increases strongly with frequency, it is scarcely possible to implement very high-frequency backscatter transponders in the GHz range, particularly with a satisfactory signal-to-noise ratio.
If, as is customary in the case of standard communication systems, a data signal is generated in the data transmitter, particularly in the transponder, with a dedicated source, the RF signal travels along the transmitter/receiver path only once. In this case, the SNR is only inversely proportional to the square of the distance. Added to this is the fact that other attenuation/losses on the transmission path also only affect the signal once and not twice. Therefore, particularly in the case of larger distances, the SNR is orders of magnitude higher in this respect than in the case of simple backscatter systems.
A device for generating an oscillator signal based on a base signal having an oscillator for actively constructing the oscillator signal via oscillations, an input for the base signal and an output for the oscillator signal generated is known from German patent document DE 100 32 822 A1 in which the oscillator is capable of being activated by the base signal to generate the oscillator signal in a quasi-phase-coherent manner with respect to the base signal. In this respect, the device comprises particularly a transmitter in the form of a transponder and provides an oscillator connected to the transponder antenna. A clock control unit is additionally provided for activating the oscillator. The oscillator is switched on and off cyclically with the clock control unit via a clock control signal. In this respect, the signal generated by the oscillator is quasi-coherent with respect to the received base signal. Switching the oscillator on and off also switches its quasi-phase-coherent activation capability.
SUMMARY
The object of the invention comprises providing a variant of a device and/or a communication system with such a device and a method for transmitting data with such a device in terms of the scope of application.
This object is achieved by a transceiver device configured for generating an oscillator signal based on a base signal, comprising: an input configured for receiving the base signal; an output configured for transmitting the oscillator signal generated; an oscillator configured for actively constructing the oscillator signal with oscillations, the oscillator configured to be activated in a quasi-phase-coherent manner aided by a control signal generated by a clock generator and configured to be activated in a quasi-phase-coherent manner with respect to the base signal via the base signal for generating the oscillator signal; the device being usable as a receiver if the oscillator is not modulated by the clock generator, and the device being usable as a transmitter if the oscillator is modulated by the clock generator in its quasi-phase-coherent activation capability and in at least one of its amplitude, phase, and frequency.
This object is further achieved by a receiver device configured for receiving and processing a quasi-phase-coherent received signal which was generated and transmitted the device of the previous paragraph, comprising: a separation apparatus configured for removing signal components of an oscillator from the quasi-phase-coherent received signal by using a base signal of a receiver-side oscillator; and a data recovery apparatus configured to recover inserted data.
This object is further achieved by a demodulator for the receiver device of the previous paragraph, comprising a phase comparator, the phase comparator comprising: an input to which a received signal originating from the mixer of the receiver is fed; a further input; and an output at which recovered data is output; the demodulator further comprising: a frequency discriminator configured to impose a frequency-dependent phase shift on an input signal, comprising: an input to which the received signal originating from the mixer of the receiver is fed; and an output connected to the further input of the phase comparator at which an output signal of the frequency discriminator is fed.
This object is further achieved by a transponder system, comprising: at least one transmitter; at least one receiver; the transponder system configured to determine a distance between the transmitter and the receiver by using a base signal transmitted from the receiver to the transmitter and a signal transmitted back from the transmitter to the receiver which is quasi-phase-coherent with respect to the base signal, at least one of the following being provided in the transmitter or the receiver: a data insertion apparatus which is adapted for inserting data or a data signal into a corresponding oscillator signal to be transmitted; and a data recovery apparatus configured to recover data inserted into received signals.
This object is further achieved by a method for transmitting data, comprising: generating an oscillator signal based on a base signal; activating an oscillator in a quasi-phase-coherent manner with respect to the base signal by way of the base signal; oscillating the oscillator in response to the activation, the oscillator actively generating a quasi-phase-coherent oscillator signal to be transmitted by way of the oscillation; and inserting data or a data signal in the quasi-phase-coherent oscillator signal to be transmitted during or following its generation.
Finally, this object is further achieved by a method for transmitting data with a device for generating an oscillator signal based on a base signal, comprising: actively constructing an oscillator signal with an oscillator configured to actively constructing the oscillator signal by way of oscillations; inputting the base signal at an input; outputting the oscillator signal at an output; generating a control signal by a clock generator; activating the oscillator in a quasi-phase-coherent manner with the aid of the control signal with respect to the base signal by way of the base signal for generating the oscillator signal; and switching the device between use as a receiver and as a transmitter; when the device is used as a receiver, not modulating the oscillator by the clock generator; and when the device is used as a transmitter, modulating the oscillator by the clock generator in its quasi-phase-coherent activation capability and in at least one of its amplitude, phase, and frequency.
According to the various embodiments of the invention discussed below, a novel active backscatter transponder and a communication system are presented which combine the advantages of various systems, i.e., make use particularly of the simple achievement of a virtually optimally small receiver bandwidth and a square-law dependency of the SNR on the distance. Furthermore, constructional solutions are provided which allow a particularly favorable implementation of the arrangement for transmitting data known as such from German patent document DE 100 32 822 A1.
Correspondingly, a device, particularly an active backscatter transponder or backscatter transponder, for generating an oscillator signal based on a base signal with an oscillator for actively constructing the oscillator signal via oscillations, an input for the base signal, and an output for the oscillator signal generated, whereby the oscillator is capable of being activated by the base signal to generate the oscillator signal in a quasi-phase-coherent manner with respect to the base signal, is advantageously equipped if it also provides a data insertion apparatus which is adapted to insert data or a data signal into the quasi-phase-coherent oscillator signal.
The data insertion apparatus advantageously comprises a clock generator, the clock pulse sequence of which is derived from the data to be inserted, and which activates the oscillator to produce a fundamental oscillation mode onto which the data is modulated. A data insertion apparatus which is adapted as a phase control apparatus, which modulates the data onto the oscillator signal by using a switchable phase shift, is also possible for inserting data, for example.
For the purposes of processing such a quasi-phase-coherent signal with inserted data received as a received signal, a device, particularly a receiver, which is appropriate, provides a separation apparatus for removing the signal components of the transmitter-side oscillator from the quasi-phase-coherent received signal by using a base signal of a receiver-side oscillator and a data recovery apparatus for recovering the inserted data.
Such a receiver is particularly advantageously equipped with a transmission mixer which provides an input for applying the signal generated by the oscillator, an output for outputting that signal as a base signal through the transmission mixer and for transmitting the base signal to an actual data transmitter station, an input for applying the received signal, and an output for outputting the mixed-down received signal, where particularly the output for outputting the base signal and the input for the received signal can coincide.
A device, particularly a transceiver in the form of a combined apparatus, which is capable of being employed as a transmitter and/or receiver depending on the purpose of use, is capable of being employed in a particularly variable manner. Such a transceiver expediently provides an oscillator for generating an oscillating signal, a clock generator for activating the oscillator, a mixer with an input for applying the oscillating signal of the oscillator, at least one interface for transmitting and/or receiving signals where the interface is connected to the mixer, at least one output of the mixer for outputting a signal received by way of the interface and mixed down with the oscillating signal, and a signal and data processing apparatus connected to the mixer.
In this respect, the signal and data processing apparatus is adapted in the form of a structural unit or a plurality of structural units and is used optionally either for applying a received base signal to the oscillator and inserting data or a data signal into the oscillating signal for subsequent output by way of the interface as the data insertion apparatus or for recovering the inserted data from a signal received by way of the interface and mixed down by way of the mixer as the data recovery apparatus.
The most diverse demodulators are capable of being employed in the receivers, particularly a demodulator with a phase comparator and a frequency discriminator for imposing a frequency-dependent phase shift on the signal, to both of which the received signal originating from the mixer is fed, where the output signal of the frequency discriminator is fed to a further input of the phase comparator, the output of which phase comparator outputs the recovered data.
A further advantageous example comprises the employment of a demodulator with at least two different bandpass filter/detector sequences, the outputs of which are applied to both an adder for outputting a measure for the signal level and also a differential amplifier followed by a series-connected comparator for outputting the reconstructed data.
Transponder systems which operate with such quasi-phase-coherent signals can also be used advantageously for transmitting data. In this respect, such a transponder system can enable the transmission of data in only one of the two directions or even in both directions. Such a transponder system provides, in a very complex form with at least one transmitter and at least one receiver in each case for determining the distance between the transmitter and the receiver by using a base signal transmitted from the receiver to the transmitter and a signal transmitted back from the transmitter to the receiver which is quasi-phase-coherent with respect to the base signal, correspondingly provided in the transmitter or the receiver, a data insertion apparatus which is adapted for inserting data or a data signal into the corresponding oscillator signal to be transmitted and/or a data recovery apparatus for recovering data inserted into received signal.
A corresponding receiver for such a distance-determining transponder system expediently provides a demodulator for recovering original data, a measuring apparatus for determining the distance between the transmitter and the receiver, an oscillator, which comprises a variable oscillator with regard to frequency, with which frequency-modulated signals suitable for measuring distance are capable of being generated, and a receiver mixer which is designed for mixing received signals with signals of the oscillator and which provides an output for outputting signals resulting therefrom, where the output is connected to the demodulator and the measuring apparatus.
For the purposes of operating these devices and systems, a method for transmitting data is appropriate where a signal is generated with the aid of an oscillator which is rendered capable of being activated in a quasi-phase-coherent manner via at least one control signal/clock signal. The oscillator rendered capable of being activated in such a way is then activated to produce oscillations in a quasi-phase-coherent manner in such a way by a received base signal that the signal generated oscillates in a quasi-phase-coherent manner with respect to the base signal. A data signal is imposed on this quasi-phase-coherent signal during or following its generation.
DESCRIPTION OF THE DRAWINGS
In the following, exemplary embodiments are explained in detail with reference to the drawing figures.
FIG. 1 is a block diagram showing an arrangement of a transmitter and a receiver where the signal of the transmitter oscillates in a quasi-phase-coherent manner with respect to signals of the receiver and data is transmitted from the transmitter to the receiver;
FIG. 2 is a block diagram showing an embodiment of a receiver illustrated by FIG. 1 ;
FIG. 3 is a block diagram showing an embodiment of a transmitter illustrated by FIG. 1 ;
FIG. 4 is a block diagram showing a transceiver which is capable of being employed both as such a transmitter and also as such a receiver;
FIG. 5 is a block diagram showing a first employable demodulation apparatus;
FIG. 6 is a block diagram showing a second employable demodulation apparatus;
FIG. 7 is a block diagram showing such a receiver with additional apparatuses for determining the distance of a transmitter; and
FIG. 8 is a diagram of an LTCC module with such a device.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows the basic principle of the underlying arrangement. The basic elements of the arrangement are known and explained in German patent document DE 100 32 822 A1.
As can be seen from FIG. 1 , an exemplary arrangement comprises a transmitter S and a receiver E. The transmitter S generates data Dat TX which is to be transmitted with a signal s by way of an interface V, particularly a radio interface, to the receiver E.
In the receiver E, an auxiliary carrier signal sH is generated with the aid of a receiver-side oscillator EHFO and, in the example shown, transmitted by using corresponding antennas ANT SE and ANT S by way of the interface V to the transmitter S.
In the transmitter S, a signal s is generated by using a transmitter-side active oscillator SHFO which signal oscillates in a quasi-phase-coherent manner with respect to the received auxiliary carrier signal sH and onto which the data to be transmitted Dat TX is or was modulated.
On the transmitter side, the auxiliary signal sH of the receiver E which was generated with the oscillator EHFO and transmitted by way of the antenna ANT SE is received with the antenna ANT S . The oscillator SHFO is switched on and off cyclically with a clock control unit TGEN as a function of the data stream Dat TX by way of the signal S 01 . In the case of suitable selection of the signal S 01 and application of the auxiliary carrier signal sH, the signal s generated by the oscillator SHFO is then, as known and described in German patent document DE 100 32 822 A1, quasi-coherent or quasi-phase-coherent with respect to the auxiliary carrier signal sH.
The signal s generated in the transmitter S, particularly a transponder, is transmitted back to the receiver and received by this receiver with the antenna ANTE. The signal e received in the receiver E, which corresponds to the transmitter signal s apart from influences during transmission, is mixed with a component of the signal generated continuously by the oscillator EHFO in the mixer MIX. Mixed components of no interest and/or interference signal and noise components are suppressed with a filter BP 1 which is preferably connected in series after the output of the mixer MIX. This filter BP 1 is preferably implemented as a bandpass filter where the center frequency and the bandwidth of the filter should be matched to the clock signal of TGEN.
The transmitter S provides the oscillator SHFO connected to the antenna ANT S . The clock control unit TGEN is additionally provided for activating the oscillator SHFO. The oscillator SHFO is alternately switched on and off and rendered capable of activation in a quasi-phase-coherent manner with the clock control unit by way of the signal S 01 . The signal s generated by the oscillator SHFO is generated in a quasi-coherent manner with respect to the auxiliary carrier signal sH by applying the received auxiliary carrier signal sH. Switching the oscillator SHFO on and off also switches its quasi-phase-coherent activation capability.
The oscillator SHFO is advantageously adapted in such a way that on the one hand, it is not activated to oscillate by thermal noise, and on the other hand, the received or auxiliary carrier signal sH injected into it is sufficient to activate quasi-phase-coherent oscillations with respect to the auxiliary carrier signal sH. In this respect, quasi-phase-coherent also particularly means that the phase difference between the auxiliary carrier signal and the generated comparison signal remains small during a turn-on period of the signal S 01 where the term “small” must be seen in relation to the intended communication or measuring task. The value Π/10, that is to say approx. 20°, can be used as the limit for a small phase divergence, for example. Such signals with only small phase divergences are described here as quasi-phase-coherent and the period of time in which this coherence exists as the coherence period.
It is appropriate in this respect that not only are the oscillations of the active oscillator SHFO quasi-phase-coherent with respect to the auxiliary carrier signal sH but that the activation of the active oscillator SHFO already takes place in a quasi-phase-coherent manner. A relatively large component of a received or auxiliary carrier signal sH is therefore coupled to the oscillator SHFO in the transmitter S which is preferably adapted as a transponder TR. This preferably constitutes an electrical auxiliary carrier signal and a corresponding oscillator signal.
But an arrangement using optical, acoustic or other signals is also capable of being implemented in principle. The received or auxiliary carrier signal sH activates the oscillator SHFO in a quasi-phase-coherent manner to produce oscillations, with the result that this oscillator generates an oscillator signal which is coupled out of the oscillator as the signal s and is derived by way of an output. The input for the received or auxiliary carrier signal sH and the output of the oscillator signal can be wholly or partly identical. But they can also be implemented separately from each other.
The signal s generated in the transmitter S is transmitted back to the receiver E by using the antenna ANT S and received by this receiver with the antenna ANT E .
A basic idea in the exemplary embodiments is that not only are the oscillations of the active oscillator SHFO in the transmitter S quasi-phase-coherent with respect to the auxiliary carrier signal sH, but that the activation of the active oscillator SHFO already takes place in a quasi-phase-coherent manner. Whereas in the case of early devices and methods according to the state of the art, the activation of the active oscillator SHFO is effected by way of thermal noise, and its oscillations are only rendered quasi-phase-coherent later by way of a complex control process and what is referred to as “LockIn”. In the present instance, the oscillator SHFO is already activated in a quasi-phase-coherent manner by way of the auxiliary carrier signal or already starts oscillating in a quasi-coherent manner and therefore phase coherence is immediately established automatically.
A basic idea is that an oscillator SHFO is in a delicate equilibrium in the basic state, and when it is switched on, it must then be activated to oscillate by way of an external energy supply of any nature. Only following this initial triggering does the feedback with which the oscillation is maintained become active. Thermal noise is customarily used for such an initialization of an oscillating circuit, for example. This means that an oscillator with a random phase and amplitude starts to oscillate and then oscillates at its frequency as defined by its resonant circuit.
However, if an external activation signal is injected into the oscillator during switching on, the frequency of which lies in the bandwidth of the resonant circuit and the power of which lies significantly above the noise power, the oscillator does not oscillate randomly, but synchronously with the phase of the activating base signal. Depending on the frequency difference between the activating auxiliary carrier signal sH and the oscillator signal and as a function of the phase noise of the two oscillators SHFO and EHFO in the transmitter S and in the receiver E, this quasi-phase-coherence continues to exist at least for a time.
The difference between the present design and the known passive devices and methods is in the use of an active oscillator SHFO in the transmitter S or transponder TR. Thus, the auxiliary carrier signal sH is not simply reflected back; instead, an oscillator signal s is actively constructed in a noise-free or virtually noise-free manner with a dedicated quasi-phase-coherent source before sending back. In this respect, given otherwise similar operation, the system therefore has a significantly greater range than passive backscatter transponder systems according to the state of the art.
In the case of transponder arrangements, a particular advantage is that no time, frequency, or polarization multiplexing whatsoever is necessary since the auxiliary carrier signal sH as the base signal and the oscillator signal s do not exert an influence on each other, or only exert an influence in the desired manner at the start of the initial oscillation response and, following this, are quasi-phase-coherent independently of each other.
It is advantageous if the device provides a switch TGEN for switching the quasi-phase-coherent activation capability of the active oscillator SHFO. This switch TGEN is used to put the active oscillator SHFO in a state from which it, being activated by the auxiliary carrier signal sH, can start to oscillate in a quasi-phase-coherent manner with respect to the auxiliary carrier signal sH.
The oscillations do not necessarily have to be switched on and off entirely for the purposes of switching the activation capability. If the active oscillator SHFO can oscillate with different modes, for example, a second mode can simply be switched while the first continues to oscillate. Even in the case of only one mode, the oscillation does not have to be switched off completely; instead, attenuation is sufficient as a rule with the result that the auxiliary carrier signal sH is sufficient for the next quasi-phase-coherent activation.
If the activation capability of the active oscillator SHFO is switched on again following the coherence period, the quasi-phase-coherence continues to exist for a lengthy period.
If the quasi-phase-coherent activation capability of the active oscillator is repeated cyclically in a development, the quasi-phase-coherence also continues to exist for lengthy periods. This can be achieved by the fact that the switch is adapted in such a way that it switches the active oscillator SHFO with a predefined clock pulse rate.
In this respect, the duration of the clock cycles of the clock pulse rate preferably corresponds roughly to the coherence period. But faster switching is also possible without the quasi-coherence between the base signal sH and the oscillator signal sH being lost.
If, conversely, the quasi-phase-coherence is only necessary in certain time intervals, the clock time can also be selected longer than the coherence period.
If the switching of the active oscillator SHFO is repeated cyclically and the active oscillator SHFO starts to oscillate cyclically in a quasi-phase-coherent manner with respect to the auxiliary carrier signal sH, the oscillator signal generated by the active oscillator can be regarded as a sampled duplicate of the auxiliary carrier signal sH.
According to the sampling theorem, a signal is completely described by its sampling values. Appropriately, the switch-off period of the active oscillator is not substantially longer than the switch-on period, i.e., not substantially longer than the coherence period. Observance of the sampling theorem is therefore an inherent result due to the coherence condition. In line with the sampling theorem, the phase difference between two sampling points must be smaller than 180°. This condition is less restrictive than the quasi-coherence condition. Consequently, from the information viewpoint, the signal s of the switched oscillator SHFO must be considered, in spite of the switching operation, to be a copy of the comparison signal or carries its complete information.
The activation capability of the active oscillator SHFO can be switched relatively simply if the oscillator SHFO itself is switched. Correspondingly, the device can provide a switch TGEN for switching the active oscillator SHFO on and off. Any switch which has the effect that the oscillation condition of the oscillator applies or no longer applies is suitable for switching the oscillator. Thus, for example, the amplification can be switched off, attenuation or propagation times (phases) changed, or the feedback branch interrupted in the oscillating circuit.
The active oscillator SHFO can be activated not only in its fundamental mode but also in a quasi-phase-coherent manner in one of its sub-harmonic oscillation modes. In this respect, the fundamental mode or a sub-harmonic oscillation mode of the base signal can be used for activation.
If the device is used for identification as an ID tag or for communication, the coding can be effected, for example, by the clock pulse rate and/or by way of an additional modulation unit such as a phase, frequency, or amplitude modulator with which the quasi-phase-coherent signal is modulated before sending back.
As previously outlined, the coherence period is dependent on the frequency difference between the base signal and the oscillator signal. The more exactly the frequencies coincide, the longer the phases of the signals are virtually identical. To increase the coherence period, as a result of which the clock pulse rate of the switch can also be kept small, it can be advantageous to provide mechanisms which are suitable for matching the oscillator frequency adaptively to the frequency of the base signal or auxiliary carrier signal sH.
As can be seen from the following description of individual exemplary embodiments, e.g. FIG. 1 , the system shown differs from known earlier backscatter transponders primarily in that the signal s transmitted back in modulated form is not simply reflected back passively; instead, it is actively generated anew in a quasi-phase-coherent manner and transmitted back. The basic principles and implementation variants and also typical signal processing methods of standard backscatter transponders can therefore be transferred directly to the present arrangement principle. Some particular features arise in the implementation, however, which make particularly advantageous arrangements possible as follows.
On the transmitter side, data Dat TX is, for example, modulated directly onto the phase-coherent signal or, in the case of generation of a clock signal S 01 for the oscillator SHFO, already incorporated into the clock signal S 01 .
In the receiver E, the modulated data Dat TX is demodulated out of the received signal e or s again. For this, the received signal e travels through the mixer MIX, for example, in which the influence of the underlying oscillator signal is taken out. Then bandpass filtering can be effected in the filter BP 1 , prior to its output signal ZFSig being fed to a demodulator Demod. The reconstructed data Dat RX is output at the output of the demodulator Demod.
A receiver station E of the communication system encompasses particularly advantageously what is referred to as a “transmission mixer” TRXMIX. A possible embodiment of a receiver station E with a transmission mixer TRXMIX is shown in FIG. 2 . The signal generated by the oscillator EHFO is transmitted as an auxiliary carrier sH through the transmission mixer to the actual data transmitter station S and at the same time is used to mix the modulated received signal e down into the baseband with the mixer TRXMIX. It can be seen that the advantageous method for transmitting data can be implemented with a transmission mixer TRXMIX with minimum device cost.
FIG. 3 shows a further possible embodiment for achieving the modulation with a switchable phase shift by using a phase control element PhMod in the transponder S or TR. With the phase control element PhMod, both the base signal for quasi-phase-coherent activation and also the signal generated in a quasi-coherent manner could be phase-modulated. In this respect, the modulation of the clock pulse 0/1, necessary by virtue of the principle, of the clock generator TGEN is superimposed by the phase modulation.
It is favorable in many applications to implement the base station being used as the receiver E and/or the transponder TR or transmitter S as a transceiver TC, i.e., in such a way that data can be transmitted in both directions between the stations. FIG. 4 shows a favorable implementation variant.
The arrangement comprises, for example, an antenna which is connected to the mixer TRXMIX. The mixer TRXMIX receives a base signal from an oscillator HFO. The oscillator in turn provides an input for an activation or trigger signal 0 / 1 which is fed from a clock generator TGEN. The mixer TRXMIX furthermore provides an output from which a signal received by way of the antenna and mixed down is output, to a bandpass filter BP 1 in the first instance, for example. Its output signal ZFSig is in turn fed to a demodulator Demod which provides reconstructed data Dat at its output. This data can be output direct or preferably fed to a microprocessor μP for further processing.
The microprocessor μP can exert an influence on the generation of the oscillator signal with the aid of the data received or even by itself, by way of a connection to the clock generator TGEN, for example. The feeding of data to be transmitted by way of the microprocessor μP, the clock generator TGEN, the oscillator HFO or a phase modulator connected in series ahead of the mixer TRXMIX is also possible.
If the oscillator HFO is not modulated by the clock generator TGEN with the result that it generates a continuous uniform sine-wave signal, the station TC shown is used as the receiver E. If the oscillator HFO is modulated by the clock generator in its quasi-phase-coherent activation capability and in its amplitude, phase and/or frequency, the station TC shown is used as the transmitter S. Such a transceiver TC preferably encompasses the processor μP which is used either to generate the data stream or to analyze the received data Dat.
In principle, all types of modulation such as those that are also used otherwise in the case of customary passive backscatter transponders can be applied in the present system. However, a frequency-modulated amplitude modulation where only the frequency of the switching period is varied to encode the digital characters is particularly advantageous for the principle. The clock generator TGEN then generates a first switching frequency Freq 1 for a digital “0” and a second switching frequency Freq 2 for a digital “1”, for example.
Apart from this binary FSK (Frequency Shift Keying) encoding, multi-stage encoding methods with more than 2 frequency stages are naturally also capable of being applied. The variation of the pulse/interval relationship in the case of a constant pulse or interval length can also be used for modulation. All methods of frequency modulation known as such can be used.
FIGS. 5 and 6 show implementations of FSK demodulators which are known as such in terms of the principle but which can be used very advantageously in such arrangements.
In FIG. 5 , the demodulator Demod provides a low-noise input amplifier LNA to which the signal ZFSig' is fed from the mixer or bandpass filter, for example. The signal pre-processed in this amplifier is fed both direct to a phase comparator PHKomp and also a frequency discriminator DISC. The output signal of the frequency discriminator DISC is fed to a further input of the phase comparator PHKomp. Its output signal is output from the demodulator Demod as a data stream Dat after traveling through a low-pass filter TP, for example.
In this respect, the frequency discriminator DISC is used to impose a frequency-dependent phase shift on the intermediate frequency signal ZFSig'. The frequency modulation can then be converted into a corresponding output voltage by way of phase comparison, in a mixer, for example, particularly the phase comparator PHComp. PLL circuits for frequency demodulation or other frequency-comparison arrangements are also capable of application for the method described here.
In FIG. 6 , the intermediate frequency signal ZFSig' is transmitted by way of two different bandpass filter/detector sequences, for example. The two sequences comprise a bandpass filter BP 1 or BP 2 , a rectifier G 1 or G 2 and a low-pass filter TP 1 or TP 2 in each case, for example. The output signals of these two sequences are fed to both an adder SUM and also a differential amplifier DIFF. Depending on the modulation frequency, either the one or the other filtered signal has a greater amplitude, which can be detected by way of the differential amplifier DIFF followed by a series-connected comparator SK, for example. The comparator SK outputs the reconstructed data Dat. The sum of the signals from the two filter branches constitutes a measure of the signal level SP.
The present method for transmitting data and the present arrangements can be employed or combined very well with distance-measuring transponder systems. Such transponder systems are described in the German patent application DE 101 55 251 “Transpondersystem und Verfahren zur Entfemungsmessung”, (Transponder system and method for distance measuring) for example, to the full scope of which reference is made.
FIG. 7 shows the additions necessary to expand the functionality in the case of such a distance-measuring transponder system. In place of a fixed-frequency oscillator, an oscillator HFVCO is used here which is variable with regard to frequency and with which frequency-modulated signals suitable for measuring distance can be generated. After the receiver mixer TRXMIX, which is preferably implemented as a transmission mixer as shown, the intermediate frequency signal is then preferably divided into two sub-paths. The first demodulation path described above leads from the bandpass filter BP 1 to the demodulator Demod and is used for accommodating or reconstructing data. The second, lower path leads, as a measuring path, to a measuring apparatus Meas where the intermediate frequency signal is processed for the purposes of distance measurement.
In this respect, a corresponding method is based on determining the distance between a base station E and at least one transponder (TR; S) where a signal sH or s tx (t) of a base station oscillator HFVCO is transmitted from the base station E, a phase-coherent signal with respect to this (s or s osz (t)) is generated and transmitted by using an oscillating oscillator (SHFO) on the basis of the signal sH or e rxt (t) received from the base station in the transponder, the distance is determined on the basis of the phase-coherent signal (e or s rx (t)) received from the transponder in the base station E and the oscillator for generating the phase-coherent signal is activated in a quasi-phase-coherent manner with the received signal. Added to this in the present instance is a data signal or data which is mixed into or modulated onto the signal of the transponder TP or transmitter S.
A corresponding distance-determining system for determining the distance between a base station E and at least one transponder (TR) where the base station E provides an oscillating signal source HFVCO for generating a signal and a transmission apparatus for transmitting the signal, the transponder provides a receiver apparatus for receiving the signal from the base station, an oscillator for generating a phase-coherent signal with respect to this and a transmission apparatus for transmitting the phase-coherent signal, the base station (BS) additionally provides a receiver apparatus for receiving the phase-coherent signal from the transponder and a distance-determining apparatus (TRXMIX, Demod) for determining the distance between the base station (E) and the transponder (TR; S) is characterized by the fact that the oscillator in the transponder is activated with the received signal to generate a quasi-phase-coherent signal and data is additionally modulated onto this signal.
A base station (E) for determining the distance of a transponder (TR; S) provides a distance-determining apparatus (RXMIX, BP 1 , Meas, Demod) or delivers signals to such where the base station E provides a mixer TRXMIX for mixing the quasi-phase-coherent signal received from the transponder (TR; S) and the instantaneous oscillator or transmission signal into a hybrid signal.
The distance-determining apparatus TRXMIX, BP 1 , Demod, Meas is advantageously adapted as such to form the hybrid signal ZFSig' or (S mix (t)) by way of the equasion
s mix ( t )=cos( t−ω sw +τ·(ω c +ω sw ))
where ω c is the center frequency of the base station oscillator HFVCO, ω sw is the modulation frequency of the transmission signal SH or s tx (t) of the base station E, t is the time in the time interval 0−Ts and τ is the propagation time of the signals over the distance between the base station E and the transponder (TR; S).
The distance-determining apparatus TRXMIX, BP 1 , Demod, Meas advantageously provides a demodulation apparatus Demod for reducing or eliminating changes over time in the voltage of the hybrid signal (s mix (t)) in the time interval (0−TS) between switching the measurement on and off in the base station E to generate a measuring signal (s mess (t)).
The distance-determining apparatus TRXMIX, BP 1 , Demod, Meas also advantageously provides a demodulation apparatus Demod for mixing down the hybrid signal (s mix (t)), particularly with a frequency near or identical to a clock frequency f mk , to a frequency substantially lower than the clock frequency f mk for switching the oscillator HFVCO in the transponder (TR) on and off cyclically and subsequent filtering out of high frequency components to generate a measurement signal s mess (t).
The distance-determining apparatus TRXMIX, BP 1 , Demod, Meas can furthermore be adapted to modulate the modulation frequency ω sw of the transmission signal s tx (t) of the base station E, particularly as defined by
ω sw = 2 · π · B · t T
where T is a time duration over which the frequency is detuned over the bandwidth B.
The distance-determining apparatus TRXMIX, BP 1 , Demod, Meas can also be adapted to form the resulting FMCW measurement signal s messfmcw (t) by way of the equasion
s
mess
fmcw
(
t
)
=
cos
(
ω
c
·
τ
+
2
·
π
·
B
·
t
·
τ
T
+
π
·
B
·
t
·
T
S
T
)
·
sin
(
π
·
B
·
t
·
T
S
T
)
(
π
·
B
·
t
T
)
The distance-determining apparatus TRXMIX, BP 1 , Demod, Meas can furthermore be adapted to determine the distance from the measurement frequency f mess which corresponds to the normal FMCW (Frequency Modulated Continuous Wave) measurement frequency shifted by a frequency component Δb=B*Ts/(2 T).
The distance-determining apparatus TRXMIX, BP 1 , Demod, Meas can also be aligned to perform a Fourier transformation of the amplitude-weighted measurement signal s messfmcw (t) in the frequency range with the result that edges of a left and right sideband of at least one square-wave function produced determine the distance between the base station E and the transponder (TR; S).
A transponder (TR; S) for determining its distance from a base station E appropriately provides a signal-generating apparatus for generating an oscillator signal S or s osz (t) from a transponder received signal sH or e rxt (t)=s tx (t−T/2) with an active phase-coherently activated oscillator (SHFO) and a switch apparatus (TGEN) for switching the oscillator on and off cyclically, particularly for generating the oscillator signal as defined by
s rx ( t ) = s osz ( t - τ 2 ) = sin ( ω osz · t - ( ω c + ω sw ) · τ + ϕ 0 )
where ω c is the center frequency of the oscillator HFVCO of the base station E, ω sw is the modulation frequency of the transmission signal s tx (t) of the base station E, t is the time, τ is the propagation time of the signals over the distance between the base station E and the transponder (TR) and φ 0 is any desired phase offset.
In the case of such a distance-determining system, modulation is additionally used for switching the oscillator (SHFO) in the transponder (TR; S) on and off for transmitting additional information or data from the transponder to the base station E, as is described in the foregoing on the basis of various exemplary embodiments.
If the distance-determining apparatus in the base station provides a mixer TRXMIX for mixing the quasi-phase-coherent signal received from the transponder and the instantaneous transmission signal into a hybrid signal, a measurement signal is produced which provides at least 2 spectral components whose frequency interval or phase interval constitutes a measure of the distance from the base station to the transponder where this measure is independent of the switching-on and switching-off frequency of the oscillator in the transponder.
Modulating or detuning the modulation frequency of the transmission signal of the base station ultimately results in a measurement signal which provides spectral components which are expressed by cosine functions that are amplitude-weighted. Advantageously, measurement even of small distances down to a value of zero is made possible by way of a frequency shift inherent to the described transponder. The additionally possible implementation of a Fourier transformation of the amplitude-weighted measurement signal in the frequency range results in spectral lines (sidebands) with a rectangular-shaped envelope where the outermost edges of a left and right sideband lying nearest to the modulation frequency determine the distance between the base station and the transponder.
As a result of the fact that the modulation frequency for switching the oscillator in the transponder on and off is not necessarily included in the analysis of the distance in the base station, it can be used to transmit additional information or data from the transponder to the base station.
In the case of the aforesaid applications, it is very advantageous as a rule if the radio frequency modules and particularly the transponder TR are constructed as small and compact as possible. In the case of access systems or payment systems where the transponder TR is customarily worn by a person on his or her body, the constructional size of the transponder TR, in the form of a key or a payment/entry card for example, decisively determines the convenience of wearing it, for example.
Radio frequency modules are customarily constructed on printed circuit boards made of organic materials, e.g., Teflon®-based or epoxy-based. Particularly in the case of low radio frequencies, e.g. 1 GHz-10 GHz, the desire for small constructional sizes can only be fulfilled to a very limited extent due to the coupling between the wavelength and the structure size with these materials. An alternative comprises circuits on thin-film ceramics, but their production is very cost-intensive.
Both the transponder TR and also the base station BS can therefore be implemented particularly advantageously as an LTCC (Low Temperature Cofired Ceramic) module or by using LTCC modules. Radio frequency structures on an LTCC basis are compact firstly due to the relatively high dielectric coefficient of LTCC but secondly also because the possibility exists of implementing the circuit in multi-layer technology. The manufacture of LTCC is inexpensive. Additionally, LTCC modules are capable of being placed in a manner which is viable in a mass production context.
Since the entire RF circuit or critical sub-components are capable of being integrated completely in an LTCC module, these integrated LTCC modules can be placed like standard SMT (Surface Mount Technology) devices on very inexpensive standard printed circuit boards which for their part are not necessarily RF-compliant. The possibility naturally also exists of combining the technologies and constructing LTCC sub-modules on printed circuit boards made of organic materials but which can then be substantially smaller.
An advantageous transponder TR with LTCC RF modules is shown in FIG. 8 . Integrated on the LTCC module LM are a radio frequency oscillator HFO, a bandpass filter BP 1 for filtering out interference modulation components which are produced by the switching (on/off) of the oscillator HFO with the clock pulse of a clock generator TGEN, and a radio frequency splitter or meter CNT, for example. The oscillator HFO is regulated to its target frequency by way of a control loop, to which a split-down clock pulse or the meter count is fed, as is customary in the case of embodiments as defined in FIG. 7 , for example. Only digital, comparatively low-frequency signals are led out from the LTCC module LM, apart from the connection for the antenna, with the result that this module LM can be integrated without difficulty and inexpensively in the remaining circuit.
The possible construction of the LTCC module is shown in schematic form in FIG. 8 . In this respect, the RF circuit consists of a plurality of strata or RF layers. Devices which cannot be integrated into the inner layers, primarily semiconductors, for example, are placed on the upper side of the LTCC substrate. As a placement technique, SMT (Surface Mount Technology) placement or Flip Chip placement, which are known techniques, are particularly appropriate. The LTCC module LM itself can be mounted on a standard printed circuit board LP with what is referred to as Ball-Grid or Land-Grid BG/LG technology, for example.
For the purposes of promoting an understanding of the principles of the invention, reference has been made to the preferred embodiments illustrated in the drawings, and specific language has been used to describe these embodiments. However, no limitation of the scope of the invention is intended by this specific language, and the invention should be construed to encompass all embodiments that would normally occur to one of ordinary skill in the art.
The present invention may be described in terms of functional block components and various processing steps. Such functional blocks may be realized by any number of hardware and/or software components configured to perform the specified functions. For example, the present invention may employ various integrated circuit components, e.g., memory elements, processing elements, logic elements, look-up tables, and the like, which may carry out a variety of functions under the control of one or more microprocessors or other control devices. Similarly, where the elements of the present invention are implemented using software programming or software elements the invention may be implemented with any programming or scripting language such as C, C++, Java, assembler, or the like, with the various algorithms being implemented with any combination of data structures, objects, processes, routines or other programming elements. Furthermore, the present invention could employ any number of conventional techniques for electronics configuration, signal processing and/or control, data processing and the like.
The particular implementations shown and described herein are illustrative examples of the invention and are not intended to otherwise limit the scope of the invention in any way. For the sake of brevity, conventional electronics, control systems, software development and other functional aspects of the systems (and components of the individual operating components of the systems) may not be described in detail. Furthermore, the connecting lines, or connectors shown in the various figures presented are intended to represent exemplary functional relationships and/or physical or logical couplings between the various elements. It should be noted that many alternative or additional functional relationships, physical connections or logical connections may be present in a practical device. Moreover, no item or component is essential to the practice of the invention unless the element is specifically described as “essential” “critical”. Numerous modifications and adaptations will be readily apparent to those skilled in this art without departing from the spirit and scope of the present invention.
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The invention relates to a device, especially an active backscatter transponder, for generating an oscillator signal based on a base signal. It comprises an oscillator for actively constructing the oscillator signal by oscillations, an input for the base signal and an output for the oscillator signal produced. The oscillator can be induced by the base signal to generate oscillator signal in a quasi-coherent manner to the base signal. For the transmission of data, the device further has a data insertion device for inserting data or a data signal into the oscillator signal. A corresponding suitable receiver receives and processes the received signal that was generated and transmitted by such a device as a quasi-coherent signal. A separation device removes the signal portions of the oscillator from the received signal via the base signal of a receiver-side oscillator, with a data retrieval device for retrieving the inserted data.
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[0001] This application is a continuation of U.S. patent application Ser. No. 13/191,992 filed Jul. 27, 2011, which claims priority of U.S. Provisional Application Ser. No. 61/369,331 filed Jul. 30, 2010, the disclosures of which are incorporated herein by reference.
FIELD
[0002] The embodiments disclosed herein relate to chromatography media suitable for the purification of biomolecules such as by ion exchange chromatography.
BACKGROUND
[0003] The commercial scale purification of various therapeutic biomolecules, such as monoclonal antibodies, is currently accomplished using bead-based chromatography resins. Monoclonal antibodies continue to gain importance as therapeutic and diagnostic agents. The process of screening hybridoma libraries for candidate mABs is both time consuming and labor intensive. Once a hybridoma cell line expressing a suitable mAB is established, a purification methodology must be developed to produce sufficient mAB for further characterization. A traditional method for purifying involves using Protein A or Protein G affinity chromatography, as well as ion exchange chromatography. The purified antibody is desalted and exchanged into a biological buffer using dialysis. The entire process typically requires several days to complete and can be particularly onerous if multiple mABs are to be evaluated in parallel.
[0004] Chromatography resins are currently prepared with various ligand structures that enable the beads to function in affinity, cation-exchange, or anion-exchange modes. These resins demonstrate a high porosity and large surface areas that provide materials with sufficient adsorptive capacities for the batch processing of biomolecules at production scales (e.g., 10,000 liters). Chromatography resins typically present a spherical structure that enables an efficient column packing with minimal flow non-uniformities. The interstitial spaces between the beads provide flow channels for convective transport through the chromatography column. This enables chromatography columns to be run with large bed depths at a high linear velocity with a minimal pressure drop. The combination of these factors enables chromatography resins to present the required efficiency, high permeability, and sufficient binding capacity that are required for the large-scale purification of biomolecules. In bead-based chromatography, most of the available surface area for adsorption is internal to the bead. Consequently, the separation process is inherently slow since the rate of mass transport is typically controlled by pore diffusion. To minimize this diffusional resistance and concomitantly maximize dynamic binding capacity, small diameter beads can be employed. However, the use of small diameter beads comes at the price of increased column pressure drop. Consequently, the optimization of preparative chromatographic separations often involves a compromise between efficiency/dynamic capacity (small beads favored) and column pressure drop (large beads favored).
[0005] Chromatography media typically has a very high cost (>$1000/L) and significant quantities are required for large scale production columns. As a result, biopharmaceutical manufacturers recycle chromatography resins hundreds of times. Each of these regeneration cycles consumes substantial quantities of media, and each step incurs additional costs associated with the validation of each cleaning, sterilization, and column packing operation.
[0006] Several technologies are described in the patent literature and marketed commercially for biopharmaceutical separations based on functionalized fibrous media and/or composites. Most rely on incorporating a porous gel into the fiber matrix, the gel providing the needed surface area to gain reasonable binding capacities. However, in such constructions, poor uniformity in gel location and mass generally leads to poor efficiencies (shallow breakthrough and elution fronts). In addition, resistance to flow can be high even for short bed depths, a problem often aggravated by gel compression under modest pressure loads. Another approach taken has been the incorporation of particulates within the fiber matrix, the particulates often porous and possessing a native adsorptive functionality, examples being activated carbon and silica gel.
[0007] It would be desirable to provide the combination of a high surface area fiber with pendant adsorptive functionality for biomolecule chromatography applications, without sacrificing bed permeability and attainable flow rates.
SUMMARY
[0008] The shortcomings of the prior art have been addressed by the embodiments disclosed herein, which relate to an adsorptive media for chromatography, particularly ion-exchange chromatography. The chromatography media disclosed is derived from a shaped fiber. In certain embodiments, the shaped fiber presents a fibrillated or ridged structure. These ridges can greatly increase the surface area of the fibers when compared to ordinary fibers. Thus, high surface area is obtained without reducing fiber diameter, which typically results in a significant decrease in bed permeability and a corresponding reduction in flow rate. An example of the high surface area fiber in accordance with certain embodiments is “winged” fibers, commercially available from Allasso Industries, Inc. (Raleigh, N.C.). A cross-sectional SEM image of an Allasso winged fiber is provided in FIG. 1 d . These fibers present a surface area of approximately 14 square meters per gram. Also disclosed herein is a method to add surface pendant functional groups that provides cation-exchange or anion-exchange functionality, for example, to the high surface area fibers. This pendant functionality is useful for the ion-exchange chromatographic purification of biomolecules, such as monoclonal antibodies (mAbs).
[0009] Embodiments disclosed herein also relate to methods for the isolation, purification or separation of biomolecules with media comprising a high surface area functionalized fiber. These methods can be carried out in a flow through mode or a bind/elute mode. For example, in mAb purification, cation exchange chromatography is typically conducted wherein, operating at a pH below the isoelectric point of the antibody protein and at a modestly depressed solution conductivity, the antibody protein will ionically bind to the support via the ion exchange ligand while unbound contaminants (host cell proteins, nucleic acids, etc.) pass freely through the chromatography bed. These contaminants are further eliminated by flushing the packed bead bed with appropriate buffer solution before releasing the bound mAb product with a buffer of high conductivity sufficient to shield the ionic interaction between bead resin and protein. In contrast, anion exchange chromatography is often used downstream in monoclonal antibody production to further remove residual cell culture contaminants wherein the operation is conducted at solution conditions of pH and conductivity such that the mAb protein will not bind to the cationic surface of the bead resin but instead passes freely through the chromatography column. Proteins and nucleic acids on the other hand that bear a net negative charge will effectively bind to the anion exchange resin and thereby are eliminated from the product.
[0010] In accordance with certain embodiments, the media disclosed herein have high bed permeability (e.g., 500-900 mDarcy), low material cost relative to bead-based chromatographic media, 20-60 mg/mL IgG dynamic binding, high separation efficiencies (e.g., HETP<0.1 cm), 50-160 mg/g IgG static binding capacity, and fast convective dominated transport of adsorbate to ligand binding sites.
[0011] In accordance with certain embodiments, the use of unique high surface area, extruded fibers (e.g., thermoplastic fibers) allows for high flow permeability (liquid) and uniform flow distribution when configured as a packed bed of randomly oriented cut fibers of lengths between 2-6 mm. Chemical treatment methods to functionalize such fiber surfaces are provided to enable bio-molecular and biological separations based on adsorptive interaction(s). Chemical treatment method can impart a variety of surface chemical functionalities to such fibers based on either ionic, affinity, hydrophobic, etc. interactions or combinations of interactions. The combined economies of fiber production and simple surface chemical treatment processes yield an economical and readily scalable technology for purification operations in biopharmaceutical as well as vaccine production.
[0012] In accordance with certain embodiments, an adsorptive separations material is provided that allows for fast processing rates, since mass transport for solutes to and from the fiber surface is largely controlled by fluid convection through the media in contrast to bead-based media where diffusional transport dictates longer contact times and therefore slower processing rates. The ability to capture or remove large biological species such as viruses is provided, which cannot be efficiently separated using conventional bead-based media due to the steric restrictions of bead pores.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 a is a schematic view of a fiber in accordance with the prior art;
[0014] FIG. 1 b is a schematic view of a ridged fiber that can be used in accordance with certain embodiments;
[0015] FIG. 1 c is a schematic view of the fiber of FIG. 1 b with attached pendant groups in accordance with certain embodiments;
[0016] FIG. 1 d is an SEM image of a ridged fiber that can be used in accordance with certain embodiments;
[0017] FIG. 1 e is a schematic view of functionalization of fibers in accordance with certain embodiments;
[0018] FIG. 1 f is another schematic view of functionalization of fibers in accordance with certain embodiments;
[0019] FIG. 2 is a IgG breakthrough curve and elution peak for SP-functionalized media in accordance with certain embodiments;
[0020] FIG. 3 is a plot of IgG breakthrough curves for SP-functionalized media at varying velocities in accordance with certain embodiments;
[0021] FIG. 4 is a plot of IgG dynamic binding capacities at varying linear velocities in accordance with certain embodiments;
[0022] FIG. 5 is a chromatogram of a mAb challenge test in accordance with certain embodiments;
[0023] FIG. 6 is a mAb elution peak for functionalized media in accordance with certain embodiments;
[0024] FIGS. 7 a, b and c show IgG quantification by a Protein A HPLC in accordance with certain embodiments;
[0025] FIGS. 8 a, b and c show ELISA data for CHO-HCP in accordance with certain embodiments;
[0026] FIG. 9 is a graph showing flow through aggregate clearance of a monoclonal antibody feed in accordance with certain embodiments;
[0027] FIG. 10 is a plot of an IgG breakthrough curve for a SP-tentacle functionalized media in accordance with certain embodiments;
[0028] FIG. 11 is a plot of IgG breakthrough curves for SP-tentacle functionalized cation-exchange media at varying velocities in accordance with certain embodiments; and
[0029] FIG. 12 is a plot of IgG dynamic binding capacities for SP-tentacle functionalized cation exchange media at varying velocities in accordance with certain embodiments.
DETAILED DESCRIPTION
[0030] The shaped fiber medium in accordance with the embodiments disclosed herein relies only on the surface of the fiber itself. Since the shaped fiber affords high surface area as well as high permeability to flow, embellishments such as the addition of a hydrogel or porous particulates are not necessary to meet performance objectives with respect to capacity and efficiency. Moreover, without the need to enhance surface area by the addition of a hydrogel or porous particulate, the manufacturing cost of the media described herein is kept to a minimum.
[0031] Fibers may be of any length and diameter and are preferably cut or staple fibers or a non-woven fabric. They need not be bonded together as an integrated structure but can serve effectively as individual discrete entities. They may be in the form of a continuous length such as thread or monofilament of indeterminate length or they may be formed into shorter individual fibers such as by chopping fibrous materials (e.g., staple fibers) such as non-woven or woven fabrics, cutting the continuous length fiber into individual pieces, formed by a crystalline growth method and the like. Preferably the fibers are made of a thermoplastic polymer, such as polypropylene, polyester, polyethylene, polyamide, thermoplastic urethanes, copolyesters, or liquid crystalline polymers. Fibers with deniers of from about 1-3 are preferred. In certain embodiments, the fiber has a cross-sectional length of from about 1 μm to about 100 μm and a cross-sectional width of from about 1 μm to about 100 μm. One suitable fiber has a cross-sectional length of about 20 μm and a cross-sectional width of about 10 μm, resulting in a denier of about 1.5. Fibers with surface areas ranging from about 100,000 cm 2 /g to about 1,000,000 cm 2 /g are suitable. Preferably the fibers have a cross-sectional length of about 10-20 μm.
[0032] In certain embodiments, the fibers can readily be packed under compression into a device or container with appropriate ports and dimensions to suit the applications described. The fibers also can be used in a pre-formed bed format such as nonwoven sheetstock material created by a spunbond (continuous filament) or wet-laid (cut fiber) process, common in the nonwovens industry. Suitable pre-formed fiber formats include sheets, mats, webs, monoliths, etc.
[0033] In certain embodiments, the fiber cross-section is generally winged-shaped, with a main body region defining a substantially longitudinal axis, and a plurality of projections extending radially outwardly from the main body region. The projections form an array of co-linear channels that extend along the length of the fiber, typically 20-30 such channels per fiber. In certain embodiments, the length of the projections is shorter than the length of the main body region. In certain embodiments, the fiber cross-section is generally winged-shaped, with a middle region comprising a longitudinal axis that runs down the center of the fiber and having a plurality of projections that extend from the middle region ( FIG. 1 d ). In certain embodiments, a plurality of the projections extends generally radially from the middle region. As a result of this configuration, a plurality of channels is defined by the projections. Suitable channel widths between projections range from about 200 to about 1000 nanometers. Suitable fibers are disclosed in U.S. Patent Publication No. 2008/0105612, the disclosure of which is incorporated herein by reference.
[0034] The surface functionalization of the high surface area fibers can be accomplished by a two step process. A suitable functionalization process is grafting polymerization, and is illustrated in Scheme 1 shown in FIG. 1 e . The functionalization begins with the attachment of pendant allyl groups to the nylon6 fiber surface by treatment of the fibers with allyl glycidyl ether in the presence of aqueous sodium hydroxide at 50° for 12 hours. The pendant allyl groups serve as anchoring sites on the fiber surface as attachment points for the pendant acrylamide polymer functionality. Conditions for the solution polymerization of acrylamide monomers are provided, and the pendant allyl groups on the fiber surface attach to the growing polymer chains in solution. Thus, the allyl-functionalized fibers are subsequently treated with an aqueous solution of 2-acrylimido-2-methyl-1-propane sulfonic acid, N,N-dimethylacrylimide and ammonium persulfate at 80° C. for 4 hours. Upon heating to 80° C., persulfate decomposition initiates a free radical polymerization of the acrylic monomers. Under these conditions, the pendant allyl groups on the fiber surface serve as attachment points for the pendant acrylic polymer functionality. In this way, the acrylic polymer is covalently attached to the fiber surface.
[0035] In certain embodiments, the acrylamide polymer may be prepared separately, and later applied to the nylon fibers as a surface coating. The resulting surface-coated fibers demonstrated comparable IgG binding capacities to the allyl grafted materials.
[0036] In accordance with certain embodiments, the functionalization begins with the deposition of a cross-linked coating of hydroxypropylacrylate (HPA) and N,N′-methylenebis(acrylamide) (MBAm) onto the surface of the high surface area fibers, as illustrated in FIG. 1 f . This step provides a reactive hydroxylalkyl functionality for a subsequent ceric ion initiated redox polymerization of an acrylamide monomer.
[0037] The HPS/MBAm treated fibers are reacted with an aqueous solution of 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt, ammonium cerium(IV) nitrate, and HNO 3 at 35° C. under a nitrogen atmosphere. Under these conditions, cerium oxidation of the crosslinked hydroxylalkyl (hydroxypropylacrylate) functionality on the fiber surface generates free radicals on the fiber surface and initiates a surface grafting polymerization of the 2-acrylamido-2-methyl-1-propanesulfonic acid monomer. Under such conditions, the surface initiated polymerization process produces a polymeric “tentacle” of polymerized (2-acrylamido-2-methyl-1-propanesulfonic acid) monomer. In this way, the acrylamide polymer is covalently attached to the fiber surface. Such processes are known as grafting polymerizations.
[0038] A suitable column packing density of between about 0.1-0.4 g/ml, preferably about 0.32 g/ml, at a bed height of 1-5 cm will provide sufficient flow uniformity for acceptable performance in a chromatographic evaluation.
[0039] In certain embodiments, the media (functionalized packed fibers) may be delivered to the user in a dry, prepacked format, unlike bead-based media. The fibers can be fused either by thermal or chemical means to form a semi-rigid structure that can be housed in a pressure vessel. By such a construction, the media and accompanying device can be made ready-to-use. Chromatographic bead-based media is generally delivered as loose material (wet) wherein the user is required is load a pressure vessel (column) and by various means create a well-packed bed without voids or channels. Follow-up testing is generally required to ensure uniformity of packing. In contrast, in accordance with certain embodiments, no packing is required by the user as the product arrives ready for service.
[0040] The shaped fiber media offers certain advantages over porous chromatographic beads by nature of its morphology. Typically in bead-based chromatography, the rate limiting step in the separation process is penetration of the adsorbate (solute) into the depths of porous beads as controlled by diffusion; for macromolecules such as proteins, this diffusional transport can be relatively slow. For the high surface area fibers disclosed herein, the binding sites are exposed on the exterior of the fibers and therefore easily accessed by adsorbate molecules in the flow stream. The rapid transport offered by this approach allows for short residence time (high flow velocity), thereby enabling rapid cycling of the media by means such as simulated moving bed systems. As speed of processing is a critical parameter in the production of biologics, fiber-based chromatographic media as described herein has particular process advantages over conventional bead-based media.
[0041] Conventional chromatographic resins start with porous beads, typically of agarose, synthetic polymer, and silica or glass. These materials are generally of high cost: unfunctionalized agarose beads can cost between $300-$350 per liter and controlled pore glass between $600-$1000 per liter. By contrast, a nonwoven bed of high surface area fibers as described herein in the appropriate densities and thickness to achieve good chromatographic properties are estimated to cost between $20-$50 per liter. This cost advantage will raise the likelihood that this new chromatographic media can be marketed as a “disposable” technology suitably priced for use and disposable after single use or most likely after multiple cycles within one production campaign.
[0042] The surface functionalized fiber media of the embodiments disclosed herein (e.g., SP functionalized Allasso fibers, SPF1) demonstrates a high permeability in a packed bed format. Depending on the packing density, the bed permeability can range from >14000 mDarcy to less than 1000 mDarcy. At low packing density of 0.1 g/mL (1 g media/9.3 mL column volume), a bed permeability of 14200 mDarcy at a linear velocity of 900 cm/hr was measured. This value does not change over a wide velocity range (400-1300 cm/hr). Such behavior indicates that the packed fiber bed does not compress at high linear velocity. Subsequent compression of the surface functionalized fiber media (SP functionalized Allasso fibers, SPF1) to a higher packing density of 0.33 g/mL (1 g media/2.85 mL column volume), afforded a bed permeability of 1000 mDarcy at a linear velocity of 900 cm/hr. Likewise, this value of 1000 mDarcy was unchanged over a linear velocity range of 400-1300 cm/hr. Suitable packing densities include between about 0.1 and about 0.5 g/ml.
[0043] For a conventional packed-bed, ion exchange chromatography media employed for bioseparations, such as ProRes-S (Millipore Corp, Billerica, Mass.), permeability values of 1900 mDarcy were measured for a packed bed of similar dimensions to the case above (3 cm bed depth, 11 mm ID Vantage column, 2.85 mL column volume). For membrane adsorbers, typical permeability values are in the range of 1-10 mDarcy. For ProRes-S, no significant change in bed permeability was measured over a range of velocities from 400-1300 cm/hr. While this behavior was expected for a semi-rigid bead, such as ProRes-S; a more compressible media (ex. agarose beads) is expected to demonstrate significant decreases in bed permeability at high linear velocities (>200 cm/hr) due to significant compression of the packed bed.
[0044] In Table 2, IgG dynamic binding capacity data was presented for the surface functionalized fiber media (SPF1) of embodiments disclosed herein. No significant change in IgG DBC values were measured at 1, 5, 10, 50% breakthrough over a range of linear velocities from 200 cm/hr to 1500 cm/hr and there was no significant change in the shape of the IgG breakthrough curves presented in FIG. 3 .
[0045] In Table A below, IgG dynamic binding capacity data is presented for ProRes-S that was measured over a wide range of linear velocities. For this traditional, packed bed, bead-based, ion exchange chromatography media (ProRes-S), a linear velocity of 60 cm/hr is recommended to maximize DBC for bind and elute capture chromatography applications. At higher velocities (>60 cm/hr), there is a significant decrease in the IgG dynamic binding capacity. At the highest linear velocity measured (1200 cm/hr) the IgG DBC is only a fraction of that measured for the 60 cm/hr case. A significant broadening of the IgG breakthrough curves were observed when ProRes-S was operated at velocities greater than 60 cm/hr.
[0046] For applications that require very short residence times or column operations at linear velocities greater than cm/hr, and especially greater than 200 cm/hr, the SP-functionalized fiber media (SPF1) is better suited for those applications than traditional bead based chromatography resins such as ProRes-S.
[0000]
TABLE A
IgG DBC values for ProRes-S media at 1, 5, 10, and
50% breakthrough at varying linear velocities.
DBC (mg/mL)
%
60
200
200
200
400
800
1200
Breakthrough
cm/hr
cm/hr
cm/hr
cm/hr
cm/hr
cm/hr
cm/hr
1
49
29
31
22
12
8
6
5
70
34
36
32
19
11
8
10
81
38
40
36
21
12
9
50
103
82
84
80
56
32
23
[0047] Examples of the high surface area fiber surface functionalization and free radical polymerization grafting procedures are provided below.
Example 1
Surface Modification of High Surface Area Fibers with Pendant Allyl Groups
[0048] Nylon Fiber Surface Modification with Allyl Glycidyl Ether.
[0049] Into a glass bottle were added allyl glycidyl ether (28.9 g, 250 mmol), sodium sulfate (6.0 g, 42 mmol) and 4 N sodium hydroxide solution (60 mL). 4 g of loose nylon fibers (supplier, lot ID) were added to the mixture. The wet solids were heated to 50° C. for 12 hours.
[0050] After cooling to room temperature, the solids were transferred to a Buchner funnel and washed with distilled water (400 mL). The material was allowed to dry under vacuum for 30 minutes.
[0051] Obtained 9.4 g as a damp solid.
[0052] The material was used immediately in the following step.
Example 2
Free Radical Graft Polymerization of Allyl-Modified, High Surface Area Fibers with Pendant Sulfopropyl Cation-Exchange Functionality
Graft Polymerization of Allyl-Modified Nylon (AMPS/DMAM 55/45).
[0053] Into a glass bottle were added 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS, 5.02 g, 24 mmol), N,N-dimethylacrylamide (DMAM, 1.96 g, 20 mmol), ammonium persulfate (0.49 g, 2 mmol) and water (72.8 mL). 9.4 g of loose nylon fibers (Example 1) were added to the mixture. The wet solids were heated to 80° C. for 4 hours.
[0054] After cooling to room temperature, the solids were transferred to a Buchner funnel and washed with distilled water (450 mL) and methanol (250 mL). The material was placed in an oven to dry at 70° C. for 12 hrs.
[0055] Obtained 4.0 g as a white fibrous solid.
Example 3
Functional Performance of the Resulting Media
[0056] The sulfopropyl-functionalized high surface area fibers from Example 2 were evaluated in a cation exchange chromatography application for the purification of a polyclonal human gamma immunoglobulin (IgG). The results of static binding capacity measurements for IgG are provided in Table 1 below. In this study, the static binding capacity of a sample of the unfunctionalized “winged fiber” from Allasso Industries (lot ID 090602PA6C) was compared to samples of sulfopropyl-functionalized fibers prepared by UV-initiated polymerization processes and the thermally initiated polymer grafting process described in Examples 1 and 2 above. The thermally initiated free radical grafting procedure provided a SP-functionalized fiber media with a significantly higher static binding capacity (50-80 mg IgG/g fiber sample) than that of the UV-initiated process (10-30 mg IgG/g fiber sample) and the unfunctionalized fibers alone (20 mg IgG/g fiber sample). IgG elution studies with 1 M NaCl solution were also performed on these samples. 50-70% recovery of the bound IgG from the SP-functionalized material under these elution conditions was measured. Based on these results, the SP-functionalized fiber media demonstrates sufficient static binding capacity and salt elution properties for functional performance testing in a biomolecule chromatography application.
[0000]
TABLE 1
Static binding capacity measurement. Challenge: 2 g/L polyclonal
human IgG (SeraCare LifeSciences, Milford, MA) in 50 mM Sodium
Acetate (pH 5). Wash buffer 50 mM Sodium Acetate (pH 5). Elution
buffer 1M sodium chloride in 50 mM Sodium Acetate (pH 5).
IgG
IgG
%
Amt
bound
SBC
eluted
recov-
Sample ID
Process
(g)
(mg)
(mg/g)
(mg)
ery
unfunctionalized
—
0.1 g
1.8
18
0.7
41%
Allasso
unfunctionalized
—
0.1 g
2.1
21
0.2
10%
Allasso
SP-funct. Allasso
UV
0.1 g
2.7
27
2.3
85%
SP-funct. Allasso
UV
0.1 g
1.2
12
2.3
190%
SP-funct. Allasso
graft
0.1 g
7.9
79
3.8
47%
(Example 2)
SP-funct. Allasso
graft
0.1 g
7.0
70
3.3
47%
(Example 2)
SP-funct. Allasso
graft
0.1 g
6.2
53
4.3
69%
(Example 2)
SP-funct. Allasso
graft
0.1 g
5.6
48
2.6
46%
(Example 2)
Example 4
[0057] Approximately 0.3 g of loose SP-functionalized Allasso winged fibers were loaded into a 6.6 mm ID Omnifit chromatography column. The bed volume was adjusted to 2 cm by compression of the top solvent distribution header to give a column volume of 0.68 mL. IgG dynamic binding capacity measurements were performed according to the following procedure:
[0000] 10 CV 50 mM NaOAc buffer (pH 5) (equilibration)
60 CV 2 mg/mL IgG (SeraCare) in 50 mM NaOAc buffer (pH 5) (IgG challenge)
80 CV 50 mM NaOAc buffer (pH 5) (wash)
50 CV 1 M NaCl in 50 mM NaOAc buffer (pH 5) (elution)
20 CV 0.5 M NaOH (cleaning)
60 CV 50 mM NaOAc buffer (pH 5) (wash)
[0058] FIG. 2 provides an example of a typical IgG breakthrough curve for the SPF1 fibers described in example 2 in accordance with certain embodiments. There is a sharp breakthrough curve and IgG dynamic binding capacities were measured ranging between 20 and 30 mg/mL (Table 2). Quantitative recovery of the bound IgG upon elution with 1 M sodium chloride in 50 mM NaOAc buffer (pH 5) was achieved.
[0000]
TABLE 2
IgG DBC values for the SP functionalized media of example 2 (SPF1) at 1, 5, 10, and 50%
breakthrough at varying linear velocities.
DBC (mg/mL)
% Breakthrough
200 cm/hr
400 cm/hr
600 cm/hr
800 cm/hr
1000 cm/hr
1500 cm/hr
1
25
23
24
24
24
23
5
26
25
26
25
25
25
10
28
27
27
27
27
26
50
34
33
33
33
33
32
[0059] FIG. 3 provides overlaid IgG breakthrough curves for the SPF1 fiber media column at varying linear velocities, ranging from 200 cm/hr to 1500 cm/hr. There is no change in the shape of the breakthrough curve as linear flow velocity is increased.
[0060] FIG. 4 shows minimal change in the measured IgG dynamic binding capacity even at very high velocities (1500 cm/hr). This behavior is indicative of a system that is dominated by convective transport of IgG molecules to the ionic ligand binding site.
[0061] In contrast, traditional bead-based ion-exchange chromatography resins will show a significant decrease in dynamic binding capacity and more diffuse breakthrough curves as velocities are increased. At very high velocities, bed compression may compromise the integrity of the beads, resulting in poorer flow uniformity and decreased chromatographic performance.
Example 5
Nylon Surface Modification with Acrylamide Copolymer Coating
Solution Polymerization of AMPS/DMAM 55/45.
[0062] Into a 250 mL three-necked roundbottom flask were added 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS, 10.04 g, 48 mmol), N,N-dimethylacrylamide (DMAM, 3.92 g, 40 mmol), ammonium persulfate (0.98 g, 4 mmol) and water (146 mL). The solution was heated to 80° C. for 4 hours. After cooling to room temperature, the polymer solution was used immediately in the following step.
[0000] Nylon Fiber Surface Modification with AMPS/DMAM Polymer Coating.
[0063] Into a glass bottle were added 19 g of AMPS/DMAM 55/45 copolymer solution prepared above and 1 g of loose nylon fibers (Allasso Industries, #090602PA6C). The wet solids were heated at 80° C. for 24 hours. After cooling to room temperature, the solids were transferred to a Buchner funnel and washed with distilled water (3×50 mL) and methanol (1×50 mL). The material was allowed to dry under vacuum for 10 minutes. The material was placed in an oven to dry at 40° C. for 24 hrs.
[0064] Obtained 0.9 g as a white fibrous solid.
[0065] Static Binding Capacity Measurement.
[0066] The results of static binding capacity measurements for IgG are provided in Table 3 below. In this study, the static binding capacity of a sample of the unfunctionalized “winged fiber” from Allasso (lot ID 090602PA6C) was compared to a sample of the sulfopropyl-functionalized fibers prepared by the solution polymer coating process of this example (Example 5). In this study, the solution polymer coating procedure provided a SP-functionalized fiber media with a higher static binding capacity (30-40 mg IgG/g fiber sample) than that of the unfunctionalized fibers alone (1 mg IgG/g fiber sample). Based on these results, the SP-functional polymer fiber coating can be installed by simple coating and thermal annealing of an AMPS/DMAM copolymer solution.
[0000]
TABLE 3
Static binding capacity measurement. Challenge: 2 g/L polyclonal
human IgG (SeraCare LifeSciences, Milford, MA) in 50 mM
Sodium Acetate (pH 5).
IgG bound
SBC
Sample ID
Process
Amt (g)
(mg)
(mg/g)
unfunctionalized
—
0.1 g
0.1
1
Allasso
#090602PA6C
SP-funct. Allasso
coating
0.1 g
4.8
42
(Example 5)
SP-funct. Allasso
coating
0.1 g
3.4
32
(Example 5)
Example 6
Surface Modification of High Surface Area Fibers with Pendant Allyl Groups
[0067] Nylon Fiber Surface Modification with Allyl Glycidyl Ether.
[0068] Into a 0.5 L flask were added allyl glycidyl ether (70.7 g, 620 mmol), sodium sulfate (14.9 g, 105 mmol) and 4 N sodium hydroxide solution (350 mL). 10 g of loose nylon fibers (Allasso Industries, #090602PA6C) were added to the mixture. The wet solids were heated to 50° C. for 12 hours. After cooling to room temperature, the solids were transferred to a Buchner funnel and washed with distilled water (1.5 L) and methanol (0.5 L). The material was allowed to dry under vacuum for 30 minutes. The material was placed in an oven to dry at 50° C. for 18 hrs.
[0069] Obtained 8.8 g as a white fibrous solid.
Example 7
Free Radical Graft Polymerization of Allyl-Modified, High Surface Area Fibers with Pendant Sulfopropyl Cation-Exchange Functionality
Graft Polymerization of Allyl-Modified Nylon (AMPS/DMAM 55/45).
[0070] Into glass vials were added 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), N,N-dimethylacrylamide (DMAM), ammonium persulfate and water according to the ratios provided in Table 4 below. Loose allyl glycidyl ether-modified nylon fibers (Example 6) were added to each mixture. The wet solids were heated to 80° C. for 4 hours. After cooling to room temperature, the wet solids were each transferred to a Buchner funnel and washed with distilled water (3×50 mL) and methanol (1×50 mL). The material was placed in an oven to dry at 40° C. for 12 hrs.
[0071] The dried, surface-modified fiber samples are ready for static binding capacity measurements with an IgG challenge solution.
Static Binding Capacity Measurement.
[0072] The results of static binding capacity measurements for IgG are also provided in Table 4 below. In this study, the static binding capacity of a sample of the unfunctionalized “winged fiber” from Allasso (lot ID 090602PA6C) was compared to the samples of the sulfopropyl-functionalized fibers prepared by the thermally initiated polymer grafting process (samples A-G). In this study, the IgG static binding capacity of the SP-functionalized fiber media can be influenced by the AMPS/DMAM polymer composition and the concentration of the reaction solution. For example, samples E and G present IgG static binding capacities that are substantially higher than those of the unfunctionalized nylon fibers alone (6 mg IgG/g fiber sample) as well as the A and C samples that were prepared with a higher AMPS content.
[0000]
TABLE 4
Graft polymerization compositions and IgG static binding capacity
measurement data. Challenge: 2 g/L polyclonal human IgG (SeraCare LifeSciences, Milford,
MA) in 50 mM Sodium Acetate (pH 5).
Fiber
AMPS
DMAM
ammonium
avg. IgG
Amount
(g,
(g,
persulfate
water
Product
SBC
Sample ID
Process
(g)
mol)
mol)
(g, mol)
(mL)
(g)
(mg/g)
A
graft
0.5 g
0.9 g,
0.1 g,
0.2 g,
9 mL
0.5 g
13
4 mmol
1 mmol
1 mmol
B
graft
0.5 g
0.9 g,
0.1 g,
0.1 g,
4 mL
did not
—
4 mmol
1 mmol
0.5 mmol
isolate
C
graft
0.5 g
0.9 g,
0.2 g,
0.2 g,
19 mL
0.5 g
6
4 mmol
2 mmol
1 mmol
D
graft
0.5 g
0.3 g,
0.4 g,
0.1 g,
6 mL
did not
—
1 mmol
4 mmol
0.5 mmol
isolate
E
graft
0.5 g
0.3 g,
0.4 g,
0.1 g,
3 mL
1.3 g
114
1 mmol
4 mmol
0.5 mmol
F
graft
0.5 g
0.3 g,
0.4 g,
0.3 g,
13 mL
did not
—
1 mmol
4 mmol
1 mmol
isolate
G
graft
0.5 g
0.6 g,
0.3 g,
0.1 g,
9 mL
0.5 g
150
3 mmol
2 mmol
0.5 mmol
Allasso
—
—
—
—
—
—
—
6
#090602PA6C
[0073] Functional Performance of the Media.
[0074] The performance of the sulfopropyl-functionalized high surface area fibers from Example 2 was evaluated in the following Example for the bind and elute purification of a monoclonal antibody (mAb) by cation exchange chromatography. The mAb was provided as an eluate from a protein A column at a concentration of 6.7 mg/mL.
Example 8
Bind and Elute Purification of Monoclonal Antibodies
[0075] Column Packing.
[0076] 0.9 g of the sulfopropyl-functionalized high surface area fibers from Example 2 were slurried in 100 g isopropanol for 30 minutes. 400 mL of deionized water was added and the slurry was allowed to agitate overnight. The fiber slurry was transferred into an 11 mm ID vantage column, using a vacuum to draw excess liquid through the column and to facilitate the compression of the staple fibers. After the slurry was transferred to the column, the top header of the column was installed, and the header compressed to give a final column volume of 2.76 mL (bed compression to target performance). HETP and peak asymmetry measurements were performed using a 2 wt % acetone solution. HETP was measured to be less than 0.1 cm and peak asymmetry was measured to be less than 2.0.
[0077] mAb Purification by Cation Exchange Chromatography.
[0078] In FIGS. 5 and 6 , an example is provided of a chromatogram from a bind/elute purification of a mAb using the cation exchange media of Example 2. In this example, 0.79 CV (2.18 mL) of a protein A elution containing 6.7 mg/mL mAb (14.7 mg mAb) were applied to the column and eluted with 250 mM NaCl in 100 mM MES buffer (pH 6). The mAb elution peak was collected in 20 0.5 CV fractions (each fraction=1.38 mL). Quantification of the mAb elution fractions by measurement of the UV absorbance of each fraction at 280 nm afforded a recovery of 13.8 mg (94% yield). The IgG elution fractions were also analyzed by protein A HPLC in FIG. 7 . This analysis also provides the IgG concentration of each elution fraction. By this analysis, the mAb elution is primarily in fractions #5-9, and the mAb recovery is 90%.
[0079] In FIG. 8 , ELISA data is provided for the Chinese hamster ovary-host cell protein concentration (CHO-HCP) of each mAb elution fraction. The HCP is primarily eluted in fractions #5-9, with an average concentration of 479 ng/mL. Since the mAb challenge solution had a HCP concentration of 6944 ng/mL, a HCP clearance log reduction value (LRV) of 1.1 was calculated.
Example 9
Surface Modification of High Surface Area Fibers with Pendant Allyl Groups
[0080] Nylon Fiber Surface Modification with Allyl Glycidyl Ether.
[0081] Into a glass vial were added allyl glycidyl ether (28.8 g, 252 mmol), sodium sulfate (6.0 g, 43 mmol) and 4 N sodium hydroxide solution (60 mL). 4 g of loose nylon fibers (Allasso Industries, #090602PA6C) were added to the mixture. The wet solids were heated to 50° C. for 12 hours.
[0082] After cooling to room temperature, the solids were transferred to a Buchner funnel and washed with distilled water (0.5 L). The material was allowed to dry under vacuum for 30 minutes. The damp material was used immediately in the following step.
Example 10
Free Radical Graft Polymerization of Allyl-Modified, High Surface Area Fibers with a Pendant Trimethylammonium Anion-Exchange Functionality
Graft Polymerization of Allyl-Modified Nylon (APTAC 100).
[0083] Into a glass vial were added (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 9.1 g, 44 mmol), ammonium persulfate (0.64 g, 3 mmol), water (27 mL) and 10 g of the wet allyl glycidyl ether modified fibers from example 9 above. The solution was heated to 80° C. for 4 hours.
[0084] After cooling to room temperature, the wet solids were each transferred to a Buchner funnel and washed with distilled water (100 mL) and methanol (30 mL). The material was allowed to dry under vacuum for 120 minutes. The material was placed in an oven to dry at 50° C. for 12 hrs.
[0085] Obtained 6.1 g as a light yellow, fibrous solid.
[0086] The dried, surface-modified fiber samples are ready for static binding capacity measurements with a bovine serum albumin (BSA) challenge solution.
Example 11
Static Binding Capacity Measurement
[0087] In order to test the performance of the trimethylammonium-functionalized fibers in an anion-exchange application, BSA static binding capacity measurements were performed. The results of static binding capacity measurements for BSA are provided in Table 5 below. In this study, the static binding capacity of a sample of the trimethylammonium-functionalized fibers prepared by the thermally initiated polymer grafting process of Example 10 was recorded. The BSA static binding capacity of the trimethylammonium-functionalized fiber media from Example 10 is between 1 and 19 mg/g.
[0000]
TABLE 5
Static binding capacity measurement. Challenge: 0.5 g/L bovine serum
albumin (BSA) in 25 mM TRIS buffer (pH 8).
BSA
bound
SBC
Sample ID
Process
Amt (g)
(mg)
(mg/g)
Q-funct. fiber
graft
0.1 g
0.1
1
example 10
Q-funct. fiber
graft
0.1 g
2.0
19
example 10
Example 12
Graft Polymerization of Un-Modified Nylon Fibers
[0088] Into 6×200 mL bottles were added 3-sulfopropylmethacrylate potassium salt (3-SPMA), water, nylon fibers (Allasso Industries) and 1 M HNO 3 solution (in the amounts described in the table below). A 0.4 M solution of ammonium cerium(IV) nitrate (CAN) in 1 M HNO 3 were added to each bottle. The reaction bottles were capped and the mixtures were heated to 35° C. for 18 hours.
[0089] After cooling to room temperature, the fiber solids from each bottle were washed with a solution of 0.2 M ascorbic acid in 0.5 M sulfuric acid (3×50 mL), DI water (3×50 mL), 1 M sodium hydroxide solution (3×50 mL), DI water (3×50 mL) and acetone (1×50 mL). The material was placed in an oven to dry at 40° C. for 12 hrs.
[0090] Obtained samples of a white fibrous solid (see Table 6 for recovery and weight add-on data).
[0000]
TABLE 6
Cerium redox graft polymerization compositions and recovery data.
Allasso
3-SPMA
fiber
monomer,
CAN
HNO 3
water
Product wt,
Reaction #
(g)
g (mmol)
(mM)
(mM)
(mL)
g (% add-on)
Example
1.5 g
7.39 g (30 mmol)
8 mM
240 mM
55.5 mL
1.72 g, (+15%)
12-1
Example
1.5 g
9.24 g (38 mmol)
6 mM
180 mM
60.4 mL
1.64 g (+9%)
12-2
Example
1.5 g
7.39 g (30 mmol)
4 mM
120 mM
65.3 mL
1.54 g (+3%)
12-3
Example
1.5 g
5.54 g (23 mmol)
6 mM
180 mM
60.4 mL
1.74 g (+16%)
12-4
Example
1.5 g
7.39 g (30 mmol)
8 mM
80 mM
67.5 mL
1.56 g (+4%)
12-5
Example
1.5 g
9.24 g (38 mmol)
6 mM
60 mM
69.4 mL
1.52 g (+1%)
12-6
[0091] Static Binding Capacity Measurement.
[0092] The results of static binding capacity measurements for IgG are provided in Table 7 below. The SP-functionalized tentacle fiber media demonstrates IgG static binding capacities comparable to bead-based cation-exchange media employed in commercial biomolecule chromatography applications.
[0000]
TABLE 7
Static binding capacity measurement. Challenge:
2 g/L polyclonal human IgG (SeraCare Life Sciences,
Milford, MA) in 50 mM Sodium Acetate (pH 5).
Amt
IgG Bound
SBC
SBC
Sample
(g)
(mg)
(mg/g)
(mg/mL) 1
Example 12-1
0.111
14.6
131
43
Example 12-2
0.102
16.4
160
52
Example 12-3
0.104
10.9
105
34
Example 12-4
0.100
14.9
149
49
Example 12-5
0.108
12.6
116
38
Example 12-6
0.103
14.2
138
45
1 Based on a 0.33 g/mL fiber packing density
[0093] Dynamic Binding Capacity Measurement.
[0094] The results of IgG dynamic binding capacity measurements for the SP-functionalized fiber media of example 12-6 are provided in Table 8 below. 1.0 g of the media was packed into an 11 mm internal diameter Vantage column and compressed to a bed depth of 2.9 cm (2.75 mL column volume, 0.36 g/mL fiber packing density). The dynamic binding capacity measurements were conducted over a range of linear velocities from 60 cm/hr to 1200 cm/hr. These velocities correspond to residence times of 9 seconds to 180 seconds. The fiber media of example 12-6 demonstrates IgG dynamic binding capacities in the range of 30-40 mg/mL.
[0000]
TABLE 8
IgG DBC values for the SP-tentacle functionalized Allasso winged fiber cation-
exchange media at 1, 5, 10, and 50% breakthrough at varying linear velocities (RT =
residence time). Challenge: 2.0 g/L polyclonal human IgG (SeraCare Life Sciences,
Milford, MA) in 50 mM acetate, pH 5.
DBC (mg/mL)
Example 12-6
60 cm/hr
%
(RT
200 cm/hr
200 cm/hr
200 cm/hr
400 cm/hr
800 cm/hr
1200 cm/hr
Breakthrough
174 sec)
(RT 52 sec)
(RT 52 sec)
(RT 52 sec)
(RT 26 sec)
(RT 13 sec)
(RT 9 sec)
1
36
31
32
31
29
27
25
5
38
32
33
33
30
28
26
10
38
33
33
33
31
28
27
50
44
39
39
39
36
34
32
Example 13
Graft Polymerization of Un-Modified Nylon Fibers
[0095] Into 6×200 mL bottles were added glycidyl methacrylate (GMA), water, nylon fibers (Allasso Industries) and 1 M HNO 3 solution (in the amounts described in the table below). A 0.4 M solution of ammonium cerium(IV) nitrate (CAN) in 1 M HNO 3 were added to each bottle. The reaction bottles were capped and the mixtures were heated to 35° C. for 18 hours.
[0096] After cooling to room temperature, the fiber solids from each bottle were washed with a solution of 0.2 M ascorbic acid in 0.5 M sulfuric acid (3×50 mL), DI water (3×50 mL), 1 M sodium hydroxide solution (3×50 mL), DI water (3×50 mL) and acetone (1×50 mL). The material was placed in an oven to dry at 40° C. for 12 hrs.
[0097] Obtained samples of a white fibrous solid (see Table 9 for recovery and weight add-on data).
[0000]
TABLE 9
Cerium redox graft polymerization compositions and recovery data.
Allasso
GMA
fiber
monomer,
CAN
HNO 3
water
Product wt,
Reaction #
(g)
g (mmol)
(mM)
(mM)
(mL)
g (% add-on) 1
Example
1.5 g
0.53 g (4 mmol)
5 mmol
150 mmol
62.8 mL
1.62 g (+8%)
13-1
Example
1.5 g
1.07 g (8 mmol)
3 mmol
75 mmol
68.9 mL
2.13 g (+42%)
13-2
Example
1.5 g
0.53 g (4 mmol)
1 mmol
30 mmol
72.6 mL
1.62 g (+8%)
13-3
Example
1.5 g
0.11 g (1 mmol)
3 mmol
75 mmol
68.9 mL
1.62 g (+8%)
13-4
Example
1.5 g
0.53 g (4 mmol)
5 mmol
50 mmol
70.3 mL
1.35 g (na,
13-5
spill)
Example
1.5 g
1.07 g (8 mmol)
3 mmol
25 mmol
72.7 mL
2.01 g (+34%)
13-6
1 Calculated based on ⅓ isolated fraction
[0098] Diethylamine-Functionalization of Epoxy-Functionalized Fibers.
[0099] Into 6×250 mL bottles were added portions of the damp GMA-functionalized fibers from the example above, and a solution of 25 wt % diethylamine (aq.) (in the amounts described in the table below). The mixtures were agitated at room temperature for 3 hours.
[0100] The fiber solids were subsequently washed with DI water (3×50 mL) and ethanol (1×50 mL). The material was placed in an oven to dry at 40° C. for 12 hrs.
[0101] Obtained samples of a white fibrous solid (see Table 10 for recovery and weight add-on data).
[0000]
TABLE 10
Compositions for the modification of epoxy-functionalized
fibers with diethylamine and recovery data.
damp
GMA-
25% Et 2 N,
Product wt,
Reaction #
fiber(g)
aq. (mL)
g (% add-on) 1
Example 13-1B
3.24
100 mL
1.08 g (+8%)
Example 13-2B
4.88
100 mL
1.32 g (+32%)
Example 13-3B
1.93
100 mL
1.08 g (+8%)
Example 13-4B
3.00
100 mL
1.00 g (+0%)
Example 13-5B
3.51
100 mL
1.22 g (+22%)
Example 13-6B
4.34
100 mL
1.34 g (+34%)
1 Calculated based on ⅔ fraction of initial 1.5 g fiber charge.
[0102] Static Binding Capacity Measurement.
[0103] The results of static binding capacity measurements for BSA are provided in Table 11 below. Depending on the GMA-tentacle grafting density, the diethylamine-functionalized tentacle fiber media can demonstrate BSA static binding capacities over a wide range of values. In this series, we found the Example 13-2B and Example 13-3B compositions gave BSA SBC values comparable to bead-based anion-exchange media employed in commercial biomolecule chromatography applications.
[0000]
TABLE 11
Static binding capacity measurement. Challenge: 2 g/L
bovine serum albumin (BSA) in 25 mM tris buffer (pH 8).
Amt
BSA Bound
SBC
SBC
Sample
(g)
(mg)
(mg/g)
(mg/mL) 1
Example 13-1B
0.099
2.76
28
9
Example 13-2B
0.096
14.60
152
50
Example 13-3B
0.102
18.80
184
60
Example 13-4B
0.109
1.41
13
4
Example 13-5B
0.102
4.26
42
14
Example 13-6B
0.112
6.36
57
19
Allasso 3 kg lot
0.086
0.21
2
1
1 Based on a 0.33 g/mL fiber packing density
[0104] Dynamic Binding Capacity Measurement.
[0105] The results of BSA dynamic binding capacity measurements for the diethylamine-functionalized fiber media of Example 13-3B are provided in Table 12 below. 0.5 g of the media was packed into an 11 mm internal diameter Vantage column and compressed to a bed depth of 1.5 cm (1.42 mL column volume, 0.35 g/mL fiber packing density). The dynamic binding capacity measurement was conducted at a linear velocity of 200 cm/hr. This velocity corresponds to a residence time of 27 seconds. The fiber media of Example 13-3B demonstrates a BSA dynamic binding capacity of 30 mg/mL at 10% breakthrough.
[0000]
TABLE 12
BSA DBC values for the diethylamine-tentacle functionalized Allasso
winged fiber anion-exchange media at 1, 5, 10, and 50% breakthrough
at 200 cm/hr (RT = residence time). Challenge: 2 g/L bovine
serum albumin (BSA) in 25 mM Tris buffer (pH 8).
DBC (mg/mL)
Example 13-3B
200 cm/hr
% Breakthrough
(RT 27 sec)
1
25
5
29
10
31
50
39
Example 14
Graft Polymerization of Un-Modified Nylon Fibers
[0106] Into a 500 mL bottle were added glycidyl methacrylate (GMA, 1.70 g, 12 mmol), and water (232.8 mL). 5 g of Allasso nylon fibers were added to the solution. 1 M HNO 3 solution (7.22 mL, 7.2 mmol) were added to the reaction mixture, followed by addition of a 0.4 M solution of ammonium cerium(IV) nitrate in 1 M HNO 3 (0.602 mL, 0.240 mmol)
[0107] The reaction mixture was heated to 35° C. for 1 hour.
[0108] After cooling to room temperature, the solids were washed with DI water (3×100 mL) and the damp material (12.21 g) was used immediately in the following step.
[0109] Q-Functionalization of Epoxy-Functionalized Fibers.
[0110] Into 4×250 mL bottles were added portions of the damp GMA-functionalized fibers from the example above, and a solution of 50 wt % trimethylamine (aq.) in methanol (in the amounts described in Table 13 below). The mixtures were agitated at room temperature for 18 hours.
[0111] The fiber solids were subsequently washed with a solution of 0.2 M ascorbic acid in 0.5 M sulfuric acid (3×50 mL), DI water (3×50 mL), 1 M sodium hydroxide solution (3×50 mL), DI water (3×50 mL) and ethanol (1×50 mL). The material was placed in an oven to dry at 40° C. for 12 hrs.
[0112] Obtained samples of a white fibrous solid (see Table 13 for recovery and weight add-on data).
[0000]
TABLE 13
Compositions for the modification of epoxy-functionalized
fibers with trimethylamine and recovery data.
damp
GMA-
50% Me 3 N,
Methanol
Product wt,
Reaction #
fiber(g)
aq. (mL)
(mL)
g (% add-on)
Example 14B
2.44 g
100 mL
0 mL
1.09 g (+9%)
Example 14C
2.44 g
80 mL
20 mL
1.02 g (+2%)
Example 14D
2.44 g
50 mL
50 mL
1.04 g (+4%)
Example 14E
2.44 g
20 mL
80 mL
0.97 g (−3%)
Example 14
2.44 g
—
—
1.09 g (+9%)
[0113] Static Binding Capacity Measurement.
[0114] The results of static binding capacity measurements for BSA are provided in Table 14 below. The Q-functionalized tentacle fiber media afforded BSA static binding capacities in the range of 30 mg/mL. In this series, we found the Example 14C and Example 14D compositions gave the highest BSA SBC values, comparable to bead-based anion-exchange media employed in commercial biomolecule chromatography applications.
[0000]
TABLE 14
Static binding capacity measurement. Challenge: 2 g/L
bovine serum albumin (BSA) in 25 mM tris buffer (pH 8).
Amt
BSA Bound
SBC
SBC
Sample
(g)
(mg)
(mg/g)
(mg/mL) 1
Example 14 (unmodified
0.097
−0.09
−1
0
GMA-grafted fiber)
Example 14B
0.100
8.76
88
29
Example 14C
0.097
10.10
104
34
Example 14D
0.099
10.40
105
34
Example 14E
0.104
9.66
93
30
1 Based on a 0.33 g/mL fiber packing density
[0115] Dynamic Binding Capacity Measurement.
[0116] The results of BSA dynamic binding capacity measurements for a Q-functionalized fiber media prepared according to Example 14C are provided in Table 15 below. 1.0 g of the media was packed into an 11 mm internal diameter Vantage column and compressed to a bed depth of 3.0 cm (2.85 mL column volume, 0.35 g/mL fiber packing density). The dynamic binding capacity measurements were conducted over a range of linear velocities from 60 cm/hr to 1200 cm/hr. These velocities correspond to residence times of 9 seconds to 180 seconds. The fiber media of Example 14C demonstrates BSA dynamic binding capacities in the range of 30-40 mg/mL.
[0000]
TABLE 15
BSA DBC values for the Q-tentacle functionalized Allasso winged fiber anion-
exchange media at 1, 5, 10, and 50% breakthrough at varying linear velocities (RT =
residence time). Challenge: 2 g/L bovine serum albumin (BSA) in 25 mM Tris buffer (pH 8).
Example
DBC (mg/mL)
14C
1200 cm/hr
1200 cm/hr
%
60 cm/hr
200 cm/hr
200 cm/hr
200 cm/hr
(RT
800 cm/hr
(RT
Breakthrough
(RT 180 sec)
(RT 54 sec)
(RT 54 sec)
(RT 54 sec)
9 sec)
(RT 14 sec)
9 sec)
1
34
29
25
30
29
26
25
5
36
35
36
32
30
28
27
10
37
36
37
33
31
29
28
50
43
43
44
39
38
36
35
Example 15
Graft Polymerization of Un-Modified Nylon Fibers
[0117] Into a 500 mL bottle were added hydroxyethylmethacrylate (HEMA, 1.69 g, 13 mmol), and water (232.5 mL). 5.00 g of Allasso nylon fibers were added to the solution. 1 M HNO 3 solution (7.21 mL, 7.2 mmol) were added to the reaction mixture, followed by addition of a 0.4 M solution of ammonium cerium(IV) nitrate in 1 M HNO 3 (0.601 mL, 0.240 mmol).
[0118] The reaction mixture was heated to 35° C. for 1 hour.
[0119] After cooling to room temperature, the solids were washed with a solution of 0.2 M ascorbic acid in 0.5 M sulfuric acid (3×100 mL), DI water (3×100 mL), 1 M sodium hydroxide solution (3×100 mL), DI water (3×100 mL) and ethanol (1×100 mL). The material was placed in an oven to dry at 40° C. for 12 hrs.
[0120] Obtained 5.58 g as a white fibrous solid.
Example 16
Sulfation of Poly(HEMA)-Functionalized Fibers
[0121] Into a 500 mL 3 necked flask under argon with a magnetic stirbar and 3 N NaOH sodium hydroxide bubbler were added acetic acid and cooled to 0° C. Chlorosulfonic acid (5.0 g, 43 mmol) was added. 2.5 g of the poly(HEMA)-functionalized fibers from the above example were added to the reaction mixture. The reaction was allowed to warm to room temperature and stirred for 1 hour.
[0122] The fiber solids were subsequently neutralized by addition of 5 mL water and 300 mL 1 M sodium carbonate solution. Solid sodium carbonate was added to the reaction mixture in portions until the pH >7. The fiber solids were subsequently washed with a solution of 1 M sodium carbonate (3×100 mL), DI water (3×100 mL) and ethanol (1×100 mL). The material was placed in an oven to dry at 40° C. for 12 hrs.
[0123] Obtained 3.64 g of a white gummy solid.
Comparative Example 1
Graft Polymerization of Un-Modified EVOH Fibers
[0124] Into 4×30 mL bottles were added 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt solution (AmPS-Na, 50% aq.), water, and EVOH fibers (Engineered Fiber Technologies, S030-0.5d×5 mm). The reaction mixture was purged under vacuum and backfilled with nitrogen three times. 1 M HNO 3 solution and a 0.4 M solution of ammonium cerium(IV) nitrate (CAN) in 1 M HNO 3 were added to each bottle (in the amounts described in Table 16 below). The reaction bottles were capped and the mixtures were heated to 40° C. for 12 hours.
[0125] After cooling to room temperature, the fiber solids from each bottle were washed with DI water (3×30 mL), a solution of 0.2 M ascorbic acid in 0.5 M sulfuric acid (3×30 mL), DI water (3×30 mL), 1 M sodium hydroxide solution (2×30 mL), DI water (3×30 mL) and methanol (2×30 mL). The material was placed in an oven to dry at 40° C. for 8 hrs.
[0126] Obtained samples of a white fibrous solid (see Table 16 for recovery and % yield data).
[0000]
TABLE 16
Cerium redox graft polymerization compositions and recovery data.
EVOH
AmPS-Na
fiber
monomer,
CAN
HNO 3
water
Product wt,
Reaction #
(g)
g (mmol)
(mM)
(mM)
(mL)
g (% yield)
Comparative
0.5 g
4.58 g (20 mmol)
2.5 mmol
25 mmol
10.2 mL
0.42 g (84%)
Example 1-1
Comparative
0.5 g
2.29 g (10 mmol)
5.0 mmol
25 mmol
14.7 mL
0.45 g (90%)
Example 1-2
Comparative
0.5 g
1.15 g (5 mmol)
1.0 mmol
25 mmol
17.2 mL
0.45 g (90%)
Example 1-3
Comparative
0.5 g
0.46 g (2 mmol)
2.5 mmol
25 mmol
18.5 mL
0.43 g (86%)
Example 1-4
Comparative Example 2
Graft Polymerization of Un-Modified PVA Fibers
[0127] Into 4×30 mL bottles were added 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt solution (AmPS-Na, 50% aq.), water, and PVA fibers (Engineered Fiber Technologies, VPB 052×3 mm). The reaction mixture was purged under vacuum and backfilled with nitrogen three times. 1 M HNO 3 solution and a 0.4 M solution of ammonium cerium(IV) nitrate (CAN) in 1 M HNO 3 were added to each bottle (in the amounts described in Table 17 below). The reaction bottles were capped and the mixtures were heated to 40° C. for 12 hours.
[0128] After cooling to room temperature, the fiber solids from each bottle were washed with DI water (3×30 mL), a solution of 0.2 M ascorbic acid in 0.5 M sulfuric acid (3×30 mL), DI water (3×30 mL), 1 M sodium hydroxide solution (2×30 mL), DI water (3×30 mL) and methanol (2×30 mL). The material was placed in an oven to dry at 40° C. for 8 hrs.
[0129] Obtained samples of a white fibrous solid (see Table 17 for recovery and % yield data).
[0000]
TABLE 17
Cerium redox graft polymerization compositions and recovery data.
PVA
AmPS-Na
fiber
monomer,
CAN
HNO 3
water
Product wt,
Reaction #
(g)
g (mmol)
(mM)
(mM)
(mL)
g (% yield)
Comparative
0.5 g
4.58 g (20 mmol)
2.5 mmol
25 mmol
10.2 mL
0.45 g (90%)
Example 2-1
Comparative
0.5 g
2.29 g (10 mmol)
5.0 mmol
25 mmol
14.7 mL
0.53 g (106%)
Example 2-2
Comparative
0.5 g
1.15 g (5 mmol)
1.0 mmol
25 mmol
17.2 mL
0.44 g (88%)
Example 2-3
Comparative
0.5 g
0.46 g (2 mmol)
2.5 mmol
25 mmol
18.5 mL
0.42 g (84%)
Example 2-4
[0130] Static Binding Capacity Measurement.
[0131] The results of static binding capacity measurements for IgG are provided in Table 18 below. The SP-functionalized tentacle media based on an EVOH fiber base matrix (Comparative Example 1) demonstrates only a low IgG static binding capacity. The SP-functionalized tentacle media based on a PVA fiber base matrix (Comparative Example 2) demonstrates only a slightly higher IgG static binding capacity for certain compositions (Comparative Example 2-1). In all cases, the IgG SBC values are much lower than bead-based cation-exchange media employed in commercial biomolecule chromatography applications. These examples serve to illustrate the benefit of surface area enhancement demonstrated by the winged fiber media from Allasso Industries. If similar surface area enhancement is practiced on a PVA or EVOH type base matrix, high IgG binding capacities may be obtained after direct surface functionalization using the ceric ion redox grafting procedure described herein.
[0000]
TABLE 18
Static binding capacity measurement. Challenge:
2 g/L polyclonal human IgG (SeraCare Life Sciences,
Milford, MA) in 50 mM Sodium Acetate (pH 5).
Amt
IgG Bound
SBC
SBC
Sample
(g)
(mg)
(mg/g)
(mg/mL) 1
Comparative Example 1-1
0.111
−0.01
0
0
Comparative Example 1-2
0.098
0.35
4
1
Comparative Example 1-3
0.101
0.06
1
0
Comparative Example 1-4
0.104
−0.01
0
0
Comparative Example 2-1
0.114
1.83
16
5
Comparative Example 2-2
0.099
−0.34
−3
−1
Comparative Example 2-3
0.107
−0.12
−1
0
Comparative Example 2-4
0.108
−0.34
−3
−1
EVOH S030-0.5d 1
0.099
−0.34
−3
−1
PVA VPB052x3mm 1
0.118
0.38
3
1
1 Based on a 0.33 g/mL fiber packing density
Example 16
Nylon Fiber Surface Modification with HPA/MBAm 95/5
[0132] Into a 2000 mL 3-necked roundbottom flask with mechanical stirrer, reflux condenser, and temperature controller were added hydroxypropylacrylate (HPA, 13.7 g, 95 mmol), N,N′-methylenebis(acrylamide) (MBAm, 0.77 g, 5 mmol) and water (710 mL). 16.8 g of loose nylon fibers (Allasso Industries, #090602PA6C) were added to the mixture. Ammonium persulfate (1.60 g, 7 mmol) was added. The wet solids were heated to 80° C. for 4 hours.
[0133] After cooling to room temperature, the solids were transferred to a Buchner funnel and washed with hot water (3×500 mL) and methanol (1×500 mL). The material was allowed to dry under vacuum for 20 minutes. The material was transferred to an oven and dried at 40° C. for 18 hours.
[0134] Obtained 17.6 g as white fibers.
Example 17
Graft Polymerization of HPA/MBAm Modified Nylon Fibers
[0135] Into 4×200 mL bottles were added glycidyl methacrylate (GMA), water, HPA/MBAm modified nylon fibers (Example 16) and 1 M HNO 3 solution (in the amounts described in Table 19 below). A 0.4 M solution of ammonium cerium(IV) nitrate (CAN) in 1 M HNO 3 were added to each bottle. The reaction bottles were capped and the mixtures were heated to 35° C. for 12 hours.
[0136] After cooling to room temperature, the fiber solids from each bottle were washed with DI water (3×150 mL) and methanol (1×150 mL). The material was placed in an oven to dry at 40° C. for 12 hrs.
[0137] Obtained samples of a white fibrous solid (see Table 19 for recovery and weight add-on data).
[0000]
TABLE 19
Cerium redox graft polymerization compositions and recovery data.
GMA
HPA/MBAm
monomer,
CAN
HNO 3
water
Product wt,
Reaction #
fiber (g)
g (mmol)
(mM)
(mM)
(mL)
g (% add-on)
Example
1.5 g
5.69 g (40 mmol)
5 mM
50 mM
150 mL
3.87 g, (+158)
17-1
Example
1.5 g
3.41 g (24 mmol)
5 mM
50 mM
150 mL
2.90 g (+93%)
17-2
Example
1.5 g
1.14 g (8 mmol)
5 mM
50 mM
150 mL
2.21 g (+47%)
17-3
Example
1.5 g
0.57 g (4 mmol)
5 mM
50 mM
150 mL
1.82 g (+21%)
17-4
Example 18
Nylon Fiber Surface Modification with Recombinant Protein a Affinity Ligand, rSPA
[0138] Into a 250 mL bottle were added 1 M sodium bicarbonate (100 mL), recombinant protein A (rSPA #RN091139, 150 mg, as a 47.5 mg/mL solution in water) and water (90 mL). GMA-grafted fibers (350 mg) from the example 17-4 above were added to the reaction mixture. The mixture was heated at 37° C. for 2.5 hours.
[0139] After cooling to room temperature, the solids were transferred to a Buchner funnel and washed with 0.1 M sodium bicarbonate (3×100 mL). The wet fiber solids were suspended in 100 mL of a 10 wt % thioglycerol solution in 0.2 M sodium bicarbonate/0.5 M sodium chloride solution. The mixture was stirred at room temperature overnight.
[0140] The solids were transferred to a Buchner funnel and washed with a solution of 0.1 M TRIZMA base with 0.15 M sodium chloride (1×75 mL), 0.05 M acetic acid solution (1×75 mL). The TRIZMA base and acetic acid washing cycles were repeated two additional times. The fiber solids were finally washed with DI water (1×75 mL) and 20 wt % ethanol (1×75 mL). The fiber solids were stored in 20 wt % ethanol solution.
[0141] Static binding capacity measurement. The results of IgG static binding capacity measurements for a protein A-functionalized fiber media prepared according to example 18 are provided in Table 20 below. The protein A-functionalized tentacle fiber media afforded IgG static binding capacities in the range of 4 mg/mL. Further optimization of the protein A ligand coupling procedure will provide increased IgG static binding capacities for low-cost biomolecule affinity chromatography applications.
[0000]
TABLE 20
Static binding capacity measurement. Challenge: 2
g/L polyclonal human IgG (SeraCare Life Sciences,
Milford, MA) in phosphate buffered saline (pH 7.4).
Amt
IgG Bound
SBC
SBC
Sample
(g)
(mg)
(mg/g)
(mg/mL) 1
Example 18A
0.500
4.22
8
3
Example 18B
0.500
5.67
11
4
1 Based on a 0.33 g/mL fiber packing density
[0142] Dynamic Binding Capacity Measurement.
[0143] The results of IgG dynamic binding capacity measurements for the protein A-functionalized fiber media of example 18 are provided in Table 21 below. 0.35 g of the media was packed into an 11 mm internal diameter Vantage column and compressed to a bed depth of 1.1 cm (1.04 mL column volume, 0.34 g/mL fiber packing density). The dynamic binding capacity measurements were conducted over a range of linear velocities from 60 cm/hr to 800 cm/hr. These velocities correspond to residence times of 5 seconds to 60 seconds. The fiber media of example 18 demonstrates IgG dynamic binding capacities in the range of 5 mg/mL. Further optimization of the protein A ligand coupling procedure will provide increased IgG dynamic binding capacities for low-cost biomolecule affinity chromatography applications.
[0000]
TABLE 21
IgG DBC values for the protein A-functionalized Allasso winged fiber affinity
chromatography media at 1, 5, 10, and 50% breakthrough at varying linear velocities (RT =
residence time). Challenge: 2 g/L polyclonal human IgG (SeraCare Life Sciences, Milford, MA)
in phosphate buffered saline (pH 7.4).
Example 18
DBC (mg/mL)
%
60 cm/hr
60 cm/hr
60 cm/hr
200 cm/hr
400 cm/hr
800 cm/hr
Breakthrough
(RT 60 sec)
(RT 60 sec)
(RT 60 sec)
(RT 18 sec)
(RT 9 sec)
(RT 5 sec)
1
5
4
4
4
5
4
5
5
5
5
5
5
5
10
6
5
5
5
5
5
50
7
7
7
7
7
7
Example 19
Flow-Through Graft Polymerization of HPA/MBAm Modified Nylon Fibers
[0144] Into a 22 mm internal diameter Vantage chromatography column was added a slurry of HPA/MBAm modified nylon fibers from example 16 above (1.52 g fibers in 100 mL DI water). A vacuum was used to draw excess liquid through the column and to facilitate the compression of the staple fibers. After the slurry was transferred to the column, the top header of the column was installed, and the header compressed to give a final column volume of 4.54 mL (1.2 cm bed depth). Into a 250 mL 3-necked flask with magnetic stirbar, reflux condenser, temperature controller, and heating mantle were added 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt solution (AmPS-Na, 50% aq., 23.0 g, 100 mmol) and water (53.5 mL). The monomer solution was sparged with argon gas for 10 minutes. A 0.4 M solution of ammonium cerium(IV) nitrate (CAN) in 1 M HNO 3 (0.62 mL, 0.250 mmol) and 1 M HNO 3 solution (2.5 mL, 2.5 mmol) was added to the reaction mixture and the reaction mixture was heated to 35° C. This monomer solution was pumped through the Vantage column at a rate of 3.5 mL/min for 12 hours. The viscosity of the monomer solution was found to increase during the course of the reaction; this resulted in a substantial decrease in the flow rate of the monomer solution through the column sometime after three hours.
[0145] After cooling to room temperature, the fiber solids from the vantage column were removed and washed with a solution of 0.2 M ascorbic acid in 0.5 M sulfuric acid (3×150 mL), DI water (3×150 mL), 1 M sodium hydroxide solution (3×150 mL), DI water (3×150 mL) and methanol (1×150 mL). The material was placed in an oven to dry at 40° C. for 12 hrs.
[0146] Obtained 1.52 g as a white fibrous solid.
[0147] Static Binding Capacity Measurement.
[0148] The results of static binding capacity measurements for IgG are provided in Table 22 below. The SP-functionalized tentacle fiber media prepared through a flow-through graft polymerization process demonstrates IgG static binding capacities comparable to bead-based cation-exchange media employed in commercial biomolecule chromatography applications. The HPA/MBAm modified fiber precursor (Example 16) displays only minimal IgG SBC.
[0000]
TABLE 22
Static binding capacity measurement. Challenge:
2 g/L polyclonal human IgG (SeraCare Life Sciences,
Milford, MA) in 50 mM acetate (pH 5).
Amt
IgG Bound
SBC
SBC
Sample
(g)
(mg)
(mg/g)
(mg/mL) 1
Example 19
0.094
16.41
175
57
Example 16
0.100
0.54
5
2
(HPA/MBAm modified
fibers)
1 Based on a 0.33 g/mL fiber packing density
[0149] Dynamic Binding Capacity Measurement.
[0150] The results of IgG dynamic binding capacity measurements for the SP-functionalized fiber media of example 19 are provided in Table 23 below. 0.64 g of the media was packed into an 11 mm internal diameter Vantage column and compressed to a bed depth of 2.0 cm (1.90 mL column volume, 0.32 g/mL fiber packing density). The dynamic binding capacity measurements were conducted at a linear velocity of 200 cm/hr. This velocity corresponds to a residence time of 36 seconds. The fiber media of example 19 demonstrates an IgG dynamic binding capacity of 40 mg/mL.
[0000]
TABLE 23
IgG DBC values for the SP-tentacle functionalized Allasso winged
fiber cation-exchange media at 1, 5, 10, and 50% breakthrough
at varying linear velocities (RT = residence time, nd =
no data). Challenge: 2.0 g/L polyclonal human IgG (SeraCare
Life Sciences, Milford, MA) in 50 mM acetate, pH 5.
DBC (mg/mL)
200 cm/hr
200 cm/hr
200 cm/hr
% Breakthrough
(RT 36 sec)
(RT 36 sec)
(RT 36 sec)
1
35
34
35
5
38
37
37
10
41
40
40
50
nd
nd
59
Example 20
Graft Co-Polymerization of Un-Modified Nylon Fibers
[0151] Into 4×250 mL bottles were added glycidyl methacrylate (GMA), (3-acrylamidopropyl) trimethylammonium chloride solution (APTAC, 75 wt % solution in water), water, winged nylon fibers (Allasso Industries) and 1 M HNO 3 solution (in the amounts described in the table below). A 0.4 M solution of ammonium cerium(IV) nitrate (CAN) in 1 M HNO 3 were added to each bottle. The reaction bottles were capped and the mixtures were heated to 35° C. for 3 hours.
[0152] After cooling to room temperature, the fiber solids from each bottle were washed with acetone (3×100 mL). The damp material was placed in an oven to dry at 40° C. for 12 hrs.
[0153] Obtained samples of a white fibrous solid (see Table 24 for recovery and weight add-on data).
[0000]
TABLE 24
Cerium redox graft polymerization compositions and recovery data.
Allasso
GMA
APTAC
fiber
monomer,
monomer
CAN
HNO 3
water
Product wt,
Reaction #
(g)
g (mmol)
g (mmol)
(mM)
(mM)
(mL)
g (% add-on)
Example
1.5 g
3.84 g
0.62 g (3 mmol)
10 mM
300 mM
50.6 mL
3.13 g, (+108%)
20-1
(27 mmol)
Example
1.5 g
2.88 g
0.47 g (3 mmol)
10 mM
300 mM
50.6 mL
2.88 g
20-2
(20 mmol)
(+92%)
Example
1.5 g
1.92 g
0.31 g (2 mmol)
10 mM
300 mM
50.6 mL
2.23 g
20-3
(14 mmol)
(+49%)
Example
1.5 g
0.96 g
0.16 g (1 mmol)
10 mM
300 mM
50.6 mL
1.75 g
20-4
(7 mmol)
(+16%)
Example 21
Poly(Allylamine) Modification of Epoxy-Functionalized Fibers
[0154] Into a 30 mL bottle were added GMA/APTAC grafted fibers from Example 20-2 above (0.5 g), water (10 mL). 40 wt % poly(allylamine) hydrochloride solution (1.25 g of 40 wt % solution) and 1.0 M sodium hydroxide (10 mL). The reaction mixture was heated to 35° C. for 18 hours.
[0155] After cooling to room temperature, the solids were washed with DI water (3×50 mL) and acetone (1×50 mL).
[0156] The damp material was placed in an oven to dry at 40° C. for 12 hrs.
[0157] Obtained 0.48 g as a light yellow fibrous solid.
Example 22
Poly(Allylamine) Modification of Sulfopropyl-Functionalized Fibers
[0158] In a 500 mL beaker equipped with a magnetic stir bar were added 1.0 g of the sulfopropyl-functionalized fibers of Example 2 and a solution of polyallylamine in water (PAA MW=15 kDa, 20% (w/w), 75 mL). Poly(ethyleneglycol)diglycidyl ether (750 μL, Aldrich #475696) was added and the mixture was stirred rapidly for 5 minutes at room temperature and then quenched with 250 mL water. The mixture was filtered through a medium glass frit filter and washed with water (3×250 mL). The fibers were dried at 40° C. overnight. (Example 22)
Example 23
Poly(Allylamine) Modification of Sulfopropyl-Functionalized Fibers
[0159] In a 500 mL beaker equipped with a magnetic stir bar were added 1.0 g of the sulfopropyl-functionalized fibers of Example 2 and a solution of polyallylamine in water (PAA MW=15 kDa, 20% (w/w), 75 mL). Poly(ethyleneglycol)diglycidyl ether (750 μL, Aldrich #475696) was added and the mixture was stirred rapidly for 10 minutes at room temperature and then quenched with 250 mL water. The mixture was filtered through a medium glass frit filter and washed with water (3×250 mL). The fibers were dried at 40° C. overnight. (Example 23)
Example 24
Poly(Allylamine) Modification of Sulfopropyl-Functionalized Fibers
[0160] In a 500 mL beaker equipped with a magnetic stir bar were added 1.0 g of the poly(allylamine)-functionalized fibers of example 23 and a solution of polyallylamine in water (PAA MW=15 kDa, 20% (w/w), 75 mL). Poly(ethyleneglycol)diglycidyl ether (750 μL, Aldrich #475696) was added and the mixture was stirred rapidly for 10 minutes at room temperature and then quenched with 250 mL water. The mixture was filtered through a medium glass frit filter and washed with water (3×250 mL). The fibers were dried at 40° C. overnight. (Example 24)
[0161] Static Binding Capacity Measurement.
[0162] The results of static binding capacity measurements for BSA are provided in Table 25 below. The poly(allylamine)-functionalized fiber media afforded BSA static binding capacities in the range of 20-60 mg/mL. In this series, we found that the composition from Example 24 gave the highest BSA SBC values, comparable to bead-based anion-exchange media employed in commercial biomolecule chromatography applications.
[0000]
TABLE 25
Static binding capacity measurement. Challenge: 2 g/L
bovine serum albumin (BSA) in 50 mM tris buffer (pH 8).
Amt
BSA Bound
SBC
SBC
Sample
(g)
(mg)
(mg/g)
(mg/mL) 1
Example 22
0.01
0.60
60
20
Example 23
0.01
0.89
89
29
Example 24
0.01
1.72
172
57
Example 2
0.01
−0.03
−3
−1
1 Based on a 0.33 g/mL fiber packing density
[0163] Dynamic Binding Capacity Measurement.
[0164] The results of BSA dynamic binding capacity measurements for the poly(allylamine)-functionalized fiber media of Example 24 are provided in Table 26 below. 1.0 g of the media was packed into an 11 mm internal diameter Vantage column and compressed to a bed depth of 3.0 cm (2.85 mL column volume, 0.35 g/mL fiber packing density). The dynamic binding capacity measurement was conducted at a linear velocity of 200 cm/hr. This velocity corresponds to a residence time of 54 seconds. The fiber media of Example 24 demonstrates a BSA dynamic binding capacity of 50 mg/mL at 10% breakthrough.
[0000]
TABLE 26
BSA DBC values for the poly(allylamine)-functionalized
Allasso winged fiber anion-exchange media at 1, 5, 10,
and 50% breakthrough at 200 cm/hr (RT = residence
time). Challenge: 0.5 g/L BSA in 25 mM Tris, pH 8.
DBC (mg/mL)
Example 24
200 cm/hr
% Breakthrough
(RT 54 sec)
1
44
5
47
10
49
50
62
Example 25
Nylon Fiber Surface Modification with HPA/MBAm 95/5
[0165] Into a 1000 mL 3-necked roundbottom flask with mechanical stirrer, reflux condenser, and temperature controller were added hydroxypropylacrylate (HPA, 13.7 g, 95 mmol), N,N′-methylenebis(acrylamide) (MBAm, 0.77 g, 5 mmol) and water (710 mL). 16.8 g of loose nylon fibers (Allaso Industries, #090602PA6C) were added to the mixture. Ammonium persulfate (1.60 g, 7 mmol) was added. The wet solids were heated to 80° C. for 4 hours.
[0166] After cooling to room temperature, the solids were transferred to a Buchner funnel and washed with hot water (3×500 mL) and methanol (1×500 mL). The material was allowed to dry under vacuum for 30 minutes. The material was transferred to an oven and dried at 40° C. for 12 hours.
[0167] Obtained 17.3 g as white fibers.
Example 26
Ceric Ion Redox Graft Polymerization of HPA/MBAm Modified, High Surface Area Fibers with Pendant Sulfopropyl Cation-Exchange Functionality
[0168] Graft Polymerization of HPA/MBAm Modified Nylon Fibers.
[0169] Into a 200 mL 3-necked roundbottom flask with mechanical stirrer, reflux condenser, and temperature controller were added 2-Acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPS-Na, 23.1 g, 100 mmol), and water (76.3 mL). 2.50 g of HPA/MBAm modified nylon fibers (Example 25) were added to the solution. The reaction mixture was purged under vacuum and backfilled with nitrogen gas for 3 cycles.
[0170] A 0.4 M solution of ammonium cerium(IV) nitrate in 1 M HNO 3 (0.620 mL, 0.250 mmol) and 1 M HNO 3 solution (2.46 mL, 2.46 mmol) were added to the reaction mixture.
[0171] The reaction mixture was heated to 35° C. for 18 hours.
[0172] After cooling to room temperature, the solids were washed with a solution of 0.2 M ascorbic acid in 0.5 M sulfuric acid (3×150 mL), DI water (3×150 mL), 1 M sodium hydroxide solution (3×150 mL), DI water (3×150 mL) and acetone (3×150 mL). The material was placed in an oven to dry at 40° C. for 12 hrs.
[0173] Obtained 2.52 g as a white fibrous solid.
[0174] Functional Performance of the Media.
[0175] The sulfopropyl-functionalized high surface area fibers from Example 26 were evaluated in a cation exchange chromatography media for the purification of the polyclonal human gamma immunoglobulin (IgG).
[0176] The results of static binding capacity measurements for IgG are provided in Table 27. In this study, the static binding capacity of a sample of the unfunctionalized “winged fiber” from Allaso (lot ID “3 kg batch—no manuf. lot ID”) was compared to samples of sulfopropyl-tentacle functionalized fibers prepared by the ceric ion redox polymerization process of Example 26 and the thermally-initiated polymer grafting process described in Example 2. It was found that the ceric ion redox grafting procedure provided a SP-functionalized tentacle fiber media with a significantly higher static binding capacity (150 mg IgG/g fiber sample) than that of the thermally-initiated process (50 mg IgG/g fiber sample) and the unfunctionalized fibers alone (10 mg IgG/g fiber sample). The SP-functionalized tentacle fiber media demonstrates an IgG static binding capacity comparable to bead-based resin media employed in commercial biomolecule chromatography applications.
[0000]
TABLE 27
Static binding capacity measurement. Challenge:
2 g/L polyclonal human IgG (SeraCare LifeSciences,
Milford, MA) in 50 mM Sodium Acetate (pH 5).
Amt
IgG bound
SBC
Sample ID
Process
(g)
(mg)
(mg/g)
unfunctionalized
—
0.11 g
1.0
10
Allasso #090602PA6C
unfunctionalized
—
0.10 g
1.0
10
Allasso #090602PA6C
SP-funct. Allasso
Ce(IV)
0.10 g
16
160
Example 26
grafting
SP-funct. Allasso
Ce(IV)
0.10 g
14
140
Example 26
grafting
SP-funct. Allasso
thermal
0.12 g
6.5
56
Example 2
graft
SP-funct. Allasso
thermal
0.12 g
5.8
50
Example 2
graft
[0177] HETP values were measured using acetone injections on a 11 mm ID Vantage column packed with 1.00 g of the SP-tentacle modified nylon fibers from Example 26 with a fiber bed compressed to a bed depth of 3.0 cm (column volume 2.85 ml). Acceptable values for HETP (0.08 cm) and peak asymmetry (1.8-2.0) were found. Based on these results, it is believed that a SP-tentacle modified fiber packing density of 0.35 g/mL will provide sufficient flow uniformity for acceptable performance in a chromatographic evaluation.
[0178] IgG dynamic binding capacity measurements were also performed with this same column according to the following procedure:
[0000] 5 CV (column volume) 50 mM NaOAc buffer (pH 5) (equilibration)
60 CV 1.7 mg/mL IgG (SeraCare) in 50 mM NaOAc buffer (pH 5) (IgG challenge)
30 CV 50 mM NaOAc buffer (pH 5) (wash)
15 CV 1 M NaCl in 50 mM NaOAc buffer (pH 5) (elution)
10 CV 0.5 M NaOH (cleaning)
10 CV 50 mM NaOAc buffer (pH 5) (wash)
[0179] FIG. 10 provides an example of a typical IgG breakthrough curve for the SP-tentacle modified fibers in accordance with certain embodiments. There is a sharp breakthrough curve and IgG dynamic binding capacities of 40 mg/mL at 10% IgG breakthrough (Table 28).
[0000]
TABLE 28
IgG dynamic binding capacities for the SP-tentacle
functionalized Allasso winged fiber cation exchange media at 1, 5, 10 and 50%
breakthrough at varying linear velocities (RT = residence time).
DBC (mg/mL)
200 cm/hr
200 cm/hr
200 cm/hr
400 cm/hr
800 cm/hr
1200 cm/hr
% Breakthrough
(RT 54 sec)
(RT 54 sec)
(RT 54 sec)
(RT 27 sec)
(RT 14 sec)
(RT 9 sec)
1
39
42
43
39
36
24
5
41
45
45
42
37
26
10
42
46
47
44
39
27
50
49
53
54
52
48
32
[0180] FIG. 11 provided overlaid IgG breakthrough curves for the SP-tentacle fiber column at varying linear velocities, ranging from 200 cm/hr to 1200 cm/hr. As linear flow velocity is increased, the slope of the IgG breakthrough curves is slightly decreased. The velocity effect on dynamic IgG binding capacity for the fiber media in accordance with embodiments disclosed herein is much less pronounced than what is typically observed in bead-based systems. In FIG. 12 , only a modest decrease in the measured IgG dynamic binding capacity at the highest velocity measured (1200 cm/hr, 9 second residence time) is seen. This behavior is indicative of a system that is largely dominated by convective transport of IgG molecules to the ionic ligand binding site.
[0181] In contrast, traditional bead-based ion-exchange chromatography resins will show a significant decrease in dynamic binding capacity and more diffuse breakthrough curves as velocities are increased. At very high velocities, bed compression may compromise the integrity of the beads, resulting in poorer flow uniformity and decreased chromatographic performance.
Example 27
Flow-Through Host Cell Protein Clearance
[0182] The sulfopropyl-functionalized fiber media prepared according to Example 26 was evaluated for HCP removal activity in a flow-through polishing mode. 0.3 g of the sulfopropyl-functionalized fiber media was packed into a 14.5 mm internal diameter column and compressed to a bed depth of 0.6 cm (1.00 mL column volume, 0.30 g/mL fiber packing density). The column was tested independently and in combination with a commercial membrane adsorber (ChromaSorb™, Millipore Corp, membrane volume 0.2 mL)
[0183] A cell culture media containing monoclonal antibody was clarified and then isolated using Protein A column chromatography and the pH of the solution was adjusted to pH 5. The pH of the Protein A elution was subsequently adjusted to pH 7 with TRIS and then filtered through a 0.2 micron membrane.
[0184] The column and Chromasorb™ membrane device were equilibrated with a buffer solution (25 mM Tris at pH 7).
[0185] The sulfopropyl-functionalized fiber media and Chromasorb™ membrane adsorber were evaluated individually and in series as described in Table 29. 72 mL of the 7.3 g/L monoclonal antibody Protein A elution (pH 7) was passed through the devices at a flow rate of 0.25 mL/min. Six 12 mL factions were collected. The eight flow-through fractions as well as a pooled sample were analyzed by HCP-ELISA and protein A HPLC to determine the level of HCP clearance and the monoclonal antibody recovery, respectively.
[0186] While the SP-fibers (0.38 LRV) did not remove as much HCP as the ChromaSorb™ membrane adsorber (1.42 LRV), we found that the arrangement of the two flow-though adsorbers in series at pH 7 was more effective at HCP clearance (2.13 LRV) than either adsorber individually. Since these adsorber media are not capacity limited in this application, these results suggest that the two adsorbers are removing separate and distinct populations of HCP. We suspect that the SP-fibers would remove more HCP at a lower pH where the HCP would have a more positive effective charge, however, affinity of the monoclonal antibody for the SP-fibers would also be increased and would reduce the product recovery.
[0000]
TABLE 29
Flow through purification of a monoclonal antibody feed. Evaluation of three flow
through polishing trains. SP-fibers (Example 26) (top), ChromaSorb ™ (middle), SP-fiber
(Example 26)/ChromaSorb ™ arranged in series (bottom). Monoclonal antibody recovery
(Protein A HPLC) and HCP clearance (HCP-ELISA) for 5 flow through and 1 pooled fraction.
Challenge: 7.3 g/L of a monoclonal antibody Protein A elution (pH 7) at a flow rate of 0.25 mL/min.
Volume
Collected
mAb
Recovery
HCP
HCP
HCP
Adsorber 1
Adsorber 2
Sample #
(mL) 1
(mg/mL)
mAb
(ng/mL)
(ppm)
LRV
—
—
Protein A
—
7.31
—
616
84
—
elution
feed
SP-fibers
—
Fraction 1
12
5.08
70%
128
25
(Example 26)
Fraction 2
24
7.52
103%
276
37
Fraction 3
36
7.49
102%
272
36
Fraction 4
48
6.87
94%
294
43
Fraction 5
72
6.70
92%
243
36
Pool
—
6.59
90%
257
39
0.38
ChromaSorb ™
—
Fraction 1
12
7.09
97%
18
2
Fraction 2
24
7.14
98%
22
3
Fraction 3
36
7.10
97%
27
4
Fraction 4
48
7.62
104%
26
3
Fraction 5
72
7.14
98%
31
4
Pool
—
7.29
100%
24
3
1.42
SP-fibers
ChromaSorb ™
Fraction 1
12
4.61
63%
1
0
(Example 26)
Fraction 2
24
7.63
104%
3
0
Fraction 3
36
7.11
97%
5
1
Fraction 4
48
6.82
93%
6
1
Fraction 5
72
6.40
88%
9
1
Pool
—
7.05
96%
5
1
2.13
1 Aggregate total of flow through fraction volumes
Example 28
Flow-Through Host Cell Protein Clearance
[0187] The Q-functionalized fiber media prepared according to Example 14 (entry Example 14C) was evaluated for HCP removal activity in a flow-through polishing mode. 0.34 g of the Q-functionalized fiber media was packed into a 14.5 mm internal diameter column and compressed to a bed depth of 0.6 cm (1.00 mL column volume, 0.34 g/mL fiber packing density).
[0188] A cell culture media containing monoclonal antibody was clarified and then isolated using Protein A column chromatography and the pH of the solution was adjusted to pH 5. The pH of the Protein A elution was subsequently adjusted to pH 8 with TRIZMA base and then filtered through a 0.2 micron membrane.
[0189] The Q-functionalized fiber media column was equilibrated with a buffer solution (25 mM Tris at pH 8).
[0190] Data from the evaluation of the Q-functionalized fiber media is provided in Table 30. 100 mL of 8.2 g/L monoclonal antibody Protein A elution (pH 8) was passed through the devices at a flow rate of 1.0 mL/min. Ten 10 mL factions were collected. Bound HCP was eluted using a 1 M sodium chloride solution in 25 mM Tris pH 8 as an elution buffer. Two 10 mL elution fractions were also collected. The ten flow-through fractions and two elution fractions were analyzed by HCP-ELISA and protein A HPLC to determine the level of HCP clearance and the monoclonal antibody recovery, respectively.
[0191] The Q-functionalized fibers were effective at HCP clearance in a flow through mode. An HCP LRV of 0.3 was achieved with high mAb recovery (94%). The Q-functionalized fiber media of the embodiments disclosed herein may serve as a convenient, low cost alternative to bead-based resin media and membrane adsorber systems for flow through polishing applications in monoclonal antibody production. The high permeability of the Q-functionalized fiber media (700 mDa for a Q-functionalized fiber media prepared according to Example 14C) may enable the high speed processing of mAb feed streams at flow rates not attainable using membrane adsorbers.
[0000]
TABLE 30
Flow through purification of a monoclonal antibody feed. Evaluation of a flow
through polishing process comprising Q-functionalized fiber media in a packed bed
format (1.0 mL column volume, 0.34 g/mL packing density). Monoclonal antibody
recovery (Protein A HPLC) and HCP clearance (HCP-ELISA) for 5 flow through
and 2 elution fractions. The pooled fraction data are calculated values. Challenge:
8.2 g/L of a monoclonal antibody Protein A elution (pH 8) at a flow rate of 1.0 mL/min
(residence time = 60 seconds).
Volume
Collected
mAb
Recovery
HCP
HCP
HCP
Adsorber
Sample #
(mL) 1
(mg/mL)
mAb
(ng/mL)
(ppm)
LRV
—
Protein A
—
8.2
—
6459
790
—
elution feed
Q-fibers
Fraction 1
10
4.3
52%
1472
344
(Example 14C)
Fraction 2
20
8.1
98%
3822
474
Fraction 3
30
8.1
99%
3161
389
Fraction 4
40
8.1
99%
4022
496
Fraction 5
50
8.1
99%
3189
392
Fraction 6
60
8.1
99%
3352
412
Fraction 7
70
8.1
99%
3359
412
Fraction 8
80
8.1
99%
3405
419
Fraction 9
90
8.1
99%
3519
434
Fraction 10
100
8.1
99%
3141
386
Pool
—
7.7
94%
3244
421
0.3
Elution 1
10
0.7
—
28540
42900
Elution 2
20
0.0
—
632
0
1 Aggregate total of flow through and elution fraction volumes
Example 29
Flow-Through Monoclonal Antibody Aggregate Clearance
[0192] The sulfopropyl-functionalized fiber media prepared according to Example 26 was evaluated for monoclonal antibody aggregate removal activity in a flow-through polishing mode. 1.0 g of the sulfopropyl-functionalized fiber media was packed into a 11 mm internal diameter Vantage column and compressed to a bed depth of 3.0 cm (2.85 mL column volume, 0.35 g/mL fiber packing density).
[0193] A Protein A elution pool containing 20 g/L monoclonal antibody was diluted with a solution of 0.5 M sodium chloride in 50 mM acetate buffer (pH 5) and 50 mM acetate buffer (pH 5) to provide a 6.9 g/L solution at pH 5 and a conductivity of 19 mS/cm. A conductivity value of 19 mS/cm was selected in order to weaken the binding of monomeric monoclonal antibody and to favor the binding of aggregated monoclonal antibody species in the protein A feed solution.
[0194] The sulfopropyl-functionalized fiber media column was equilibrated with a buffer solution (50 mM acetate at pH 5).
[0195] Data from the evaluation of the sulfopropyl-functionalized fiber media is provided in Table 31 and FIG. 9 . 285 mL of 6.9 g/L monoclonal antibody Protein A elution (pH 5, 19 mS/cm) was passed through the column at a flow rate of 3.2 mL/min (200 cm/hr). Thirty-three 8.6 mL (3 column volume) factions were collected. Bound monomeric and aggregated monoclonal antibody was eluted using a 0.5 M sodium chloride solution in 50 mM acetate pH 5 as an elution buffer. Five 8.6 mL (3 column volume) elution fractions were also collected. The thirty-three flow-through fractions and five elution fractions were analyzed by size exclusion chromatography (SEC) and protein A HPLC to determine the level of aggregate clearance and the monoclonal antibody recovery, respectively.
[0196] The sulfopropyl functionalized-fibers demonstrated an ability to bind aggregated monoclonal antibody in the presence of monomeric monoclonal antibody species under a flow through mode of operation. From the Protein A HPLC data we find a high mAb recovery of 92%. Analysis of the SEC data shows a complete breakthrough of the monomeric mAb species in flow through fraction #2, while the aggregated mAb does not match the initial feed concentration of 0.6% (100% breakthrough) until flow through fraction #5. SEC analysis of the elution fractions #35, 36, and 37 show a mAb population enriched in the aggregated high molecular weight (HMW) species and depleted in monomeric mAb. The sulfopropyl-functionalized fiber media in accordance with the embodiments disclosed herein may serve as a means for aggregate clearance according to the method described in the present example. The high permeability of the sulfopropyl-functionalized fiber media (520 mDa for a sulfopropyl-functionalized fiber media prepared according to Example 26) may enable the high speed, rapid cycling of mAb feed streams at high flow rates suitable for simulated moving bed operations.
[0000]
TABLE 31
Flow through aggregate clearance of a monoclonal antibody feed. Evaluation
of a flow through aggregate clearance process comprising sulfopropyl-
functionalized fiber media in a packed bed format (2.85 mL column volume,
0.35 g/mL packing density). Monoclonal antibody recovery (Protein A HPLC)
and % monomer, % HMW aggregate (SEC) for 31 flow through and 3 elution
fractions. The pooled fraction data are calculated values. Challenge:
6.9 g/L of a monoclonal antibody Protein A elution (pH 5, 19 mS) at a flow
rate of 3.2 mL/min (residence time = 54 seconds).
%
Volume
%
HMW
Collected
mAb
Recovery
monomer
aggregate
Adsorber
Sample #
(mL) 1
(mg/mL)
mAb
(SEC)
(SEC)
—
Protein A
—
6.9
—
99.1
0.6
elution feed
sulfopropyl-
Fraction 1
8.6
0.0
0%
0.0
0.0
fibers
Fraction 2
17
5.0
73%
99.6
0.0
(Example 26)
Fraction 3
26
7.0
102%
99.4
0.4
Fraction 5
43
6.8
100%
99.1
0.6
Fraction 7
60
6.9
100%
99.1
0.6
Fraction 9
77
6.9
100%
99.1
0.6
Fraction 11
95
6.9
100%
99.1
0.6
Fraction 13
112
6.9
100%
99.1
0.6
Fraction 15
129
6.8
100%
99.1
0.6
Fraction 17
146
6.9
100%
99.1
0.6
Fraction 19
163
6.8
100%
99.1
0.6
Fraction 21
181
6.9
100%
99.1
0.6
Fraction 23
198
6.9
100%
99.1
0.6
Fraction 25
215
6.9
100%
99.1
0.6
Fraction 27
232
6.9
100%
99.1
0.6
Fraction 31
267
6.9
100%
99.1
0.6
Pool
—
6.3
92%
99.1
0.5
Elution 35
8.6
2.3
—
2.7
95.1
Elution 36
17
1.5
—
8.2
87.6
Elution 37
26
0.1
—
0.0
100
1 Aggregate total of flow through and elution fraction volumes
Example 32
Direct Capture on a Compressible Bed
[0197] The sulfopropyl-functionalized fiber media of Example 19 was evaluated for direct monoclonal antibody capture from an unclarified cell culture fluid in a flow-through mode of operation. 0.49 g of the sulfopropyl-functionalized fiber media was packed into a 14.5 mm internal diameter column and compressed to a bed depth of 3.0 cm (5.0 mL column volume, 0.10 g/mL fiber packing density). The sulfopropyl-functionalized fiber media column was equilibrated with a buffer solution (50 mM acetate at pH 5). An unclarified Chinese Hampster Ovary cell culture fluid containing 0.8 g/L monoclonal antibody was provided (pH 6.5, 5.7 mS/cm).
[0198] 100 mL of the unclarified cell culture fluid containing 0.8 g/L monoclonal antibody was passed through the column at a flow rate of 12.5 mL/min (460 cm/hr). Nine 10 mL (2 column volume) flow through factions were collected. The low density fiber bed was washed with 50 mM acetate buffer (pH 5) by repeated compression and expansion of the fiber bed. This compression and expansion was accomplished by adjustment of the column flow distribution header. Thirteen 10 mL (2 column volume) 50 mM acetate buffer (pH 5) washing factions were collected. Bound monoclonal antibody was eluted using a 1.0 M sodium chloride solution in 50 mM acetate pH 5 as an elution buffer. It is preferable to accomplish the elution step in a compressed bed format (bed depth 1.0 cm, 1.65 mL column volume, 0.30 g/mL fiber packing density) in order to further concentrate the monoclonal antibody elution. Three 10 mL (2 column volume) elution fractions were collected. The nine flow-through fractions, thirteen washing fractions and three elution fractions were analyzed by protein A HPLC to measure the monoclonal antibody recovery. Data from the evaluation of the sulfopropyl-functionalized fiber media is provided in Table 32.
[0199] The sulfopropyl-functionalized fibers demonstrated an ability to bind monoclonal antibody (mAb) in the presence of unclarified Chinese hamster ovary cell culture media. From the Protein A HPLC data, we find complete mAb breakthrough during the mAb capture operation by Fraction #7. The 50 mM acetate (pH 5) washing stage removes any unbound mAb from the column and the system by wash fraction #6. Elution with 1.0 M sodium chloride in 50 mM acetate (pH 5) elutes the bound mAb from the sulfopropyl-functionalized fiber media column. Those skilled in the art will recognize that significant gains in monoclonal IgG binding capacity may be realized by any number of process variations. These may include the reduction of cell culture feed conductivity, dilution of the unclarified cell culture feed, or the use of a Protein A affinity ligand structure instead of the sulfopropyl-based cation exchange ligand functionality of the present example. Those skilled in the art will recognize that the Protein A functionalized fiber media of Example 18, or its derivatives, may be preferred for this direct capture application. In a low packing density format, the surface functionalized fiber media is capable of direct IgG capture from unclarified feed streams. A subsequent bed compression enables the concentration of the mAb elution in a compressed bed format. This process may eliminate the use of primary (centrifugation) and secondary clarification (depth filtration) processes in the downstream processing of therapeutic biopharmaceuticals such as monoclonal antibodies.
[0000]
TABLE 32
Direct capture of a monoclonal antibody from unclarified cell
culture. Evaluation of a direct mAb capture process comprising sulfo-
propyl-functionalized fiber media in a packed bed format (5.00 mL
column volume, 0.10 g/mL packing density). Monoclonal antibody
concentration and recovery (Protein A HPLC) for 4 flow through, 4
wash and 3 sodium chloride elution fractions. Challenge: 100 mL of
an unclarified Chinese hampster ovary cell culture fluid containing
0.87 g/L of monoclonal antibody (pH 6.5, 5.7 mS) at a flow rate of
12.5 mL/min (residence time = 24 seconds).
Volume
mAb
Collected
mAb
mAb
recovery
Adsorber
Sample #
(mL) 1
(mg/mL)
C/Co
(mg)
—
unclarified
—
0.87
mAb feed
sulfopropyl-
Fraction 2
20
0.0
0.0
fibers
Fraction 5
50
0.26
0.30
(Example 19)
Fraction 7
70
0.90
1.03
Fraction 9
90
0.85
0.98
Wash 2
20
0.86
0.99
8.6
Wash 6
60
0.0
0.0
0.0
Wash 10
100
0.0
0.0
0.0
Wash 13
130
0.0
0.0
0.0
Elution 1
10
0.76
0.87
7.6
Elution 2
20
0.21
0.24
2.1
Elution 3
30
0.06
0.07
0.6
1 Aggregate total of flow through, wash and elution fraction volumes
Example 33
Fiber Media Capability for the Bind/Elute Purification of Viruses
[0200] The results of static binding capacity and elution recovery measurements for bacteriophage φ6 are provided in Table 31 below. Into 5 plastic centrifuge tubes were added the Q-functionalized tentacle fiber media of Example 14C and unfunctionalized Allasso fiber samples in the amounts described in Table 33 below. Each of the fiber samples and the control tube were equilibrated with 5 mL of 25 mM Tris buffer (pH 8, with 0.18 mg/mL HSA) with agitation for 10 minutes. The tubes were spun at room temperature in a table top centrifuge at 4000 rpm for 10 minutes to pellet the fiber media. 2.5 mL of the supernatant was removed and 2.5 mL of a 1.7×10 7 pfu/mL φ6 solution in 25 mM Tris buffer (pH 8, with 0.18 mg/mL HSA) were added to each tube. The samples were agitated at room temperature for 1 hour. Afterwards, the tubes were spun at room temperature in a table top centrifuge at 4000 rpm for 15 minutes to pellet the fiber media. 2.5 mL of the supernatant was removed and these samples were assayed for unbound φ6 by plaque-forming assay. The tubes were washed 3 times with 2.5 mL washings of 25 mM Tris buffer (pH 8, with 0.18 mg/mL HSA) with centrifugation to pellet the fiber media in between each wash and removal of 2.5 mL of the supernatant. After washing, 2.5 mL of a 1.0 M NaCl solution in 25 mM Tris buffer (pH 8, with 0.18 mg/mL HSA) were added to each tube (5 mL total volume, final NaCl concentration is 0.5 M). The samples were agitated at room temperature for 10 minutes. Afterwards, the tubes were spun at room temperature in a table top centrifuge at 4000 rpm for 10 minutes to pellet the fiber media. 2.5 mL of the supernatant was removed and these elution samples were assayed for eluted φ6 by plaque forming assay. The Q-functionalized tentacle fiber media of example 14C demonstrates a significant bacteriophage φ6 log reduction value (LRV) of 3.1 and an elution recovery yield of 40%. This performance is comparable to membrane-based anion-exchange media employed in commercial viral chromatography applications. The Q-functionalized fiber media of the present invention can be integrated into a pre-packed device format or a chromatography column for flow-through viral clearance or bind/elute viral purification applications.
[0000]
TABLE 33
Static binding capacity measurement. Challenge: 2.5
mL of 1.7 × 10 7 pfu/mL bacteriophage φ6 in
25 mM Tris (pH 8) with 0.18 mg/mL HSA. Elution buffer:
0.5M NaCl in 25 mM Tris (pH 8) with 0.18 mg/mL HSA.
φ6
Elution
% re-
Amt
φ6 titer
bound
φ6 titer
covery,
Sample
(g)
(pfu/mL)
(LRV)
(pfu/mL)
φ6
Control Tube
—
2.10 × 10 7
—
2.15 × 10 6
—
Example 14C
0.051 g
1.39 × 10 4
3.18
8.45 × 10 6
40.3%
Example 14C
0.052 g
1.65 × 10 4
3.10
8.15 × 10 6
38.8%
Allasso
0.051 g
2.09 × 10 7
0.00
8.65 × 10 5
—
non-functionalized
fibers
Allasso
0.050 g
2.32 × 10 7
−0.04
7.10 × 10 5
—
non-functionalized
fibers
|
Adsorptive media for chromatography, particularly ion-exchange chromatography, derived from a shaped fiber. In certain embodiments, the functionalized shaped fiber presents a fibrillated or ridged structure which greatly increases the surface area of the fibers when compared to ordinary fibers. Also disclosed herein is a method to add surface pendant functional groups that provides cation-exchange or anion-exchange functionality to the high surface area fibers. This pendant functionality is useful for the ion-exchange chromatographic purification of biomolecules, such as monoclonal antibodies (mAbs).
| 8
|
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